Accessories for Differential Scanning Calorimeters and Thermobalances

Analyzing & Testing

Accessories for Differential Scanning Calorimeters and Thermobalances Crucibles, Sensors, Sample Carriers, Calibration Kits for DSC, TGA and STA Systems Introduction – Table of Contents

Accessories for Thermal Analysis – DSC/DTA, TGA and STA

Thermal analysis is a powerful, well and instrument parts must be prevented meshes and baskets are available proven tool for obtaining reliable data while ensuring that the test results to accommodate specific sample on the caloric and thermophysical remain reliable and accurate. For these dimensions and densities. properties of a great variety of materials. reasons, one of our primary areas of focus is crucibles and sensors for DTA/ Lately, the demand for special crucibles To attain proper results, proficient DSC, TGA and STA instruments. has been increasing. Of course, state-of-the-art instruments are measurements can only be carried out required, featuring optimum technical This catalogue provides an overview of when the right sensor or sample carrier attributes such as high sensitivity and all such crucibles and sensors for DTA, for these special crucibles is available. resolution in the required temperature DSC, TGA and STA measurements. We have therefore listed these special range. In recent years, a rise in the You will find many different crucible cases here, often providing application development of new materials for materials listed, and a variety of types examples to demonstrate their emerging applications has been and special shapes. From among these, characteristic advantages. presenting an ongoing challenge for we can help you find the right crucible the thermal analysis industry in keeping size and material for any application, Our accessories can open up a world pace with rapidly evolving market be it standard or special. In addition of possibilities for your thermoana- needs. to standard aluminum crucibles, our lytical needs. It is our hope that this portfolio includes autoclaves with low catalogue will serve to acquaint you At NETZSCH, we always strive to to medium or high pressure-tightness, with these. If you have any questions, be a step ahead. We place as much as well as ones for determining the or if you require something specific importance on the development and oxidative-induction time (OIT) and which you cannot find in the following production of accessories as on that of solid fat index (SFI). We offer crucibles tables, please simply contact us – new instruments. Accessories in contact made of ceramics or metals covering NETZSCH welcomes the challenge of with the sample or in close proximity a wide temperature range. In the working out a solution tailored to your to it require special attention. Potential high-temperature range, special TGA application, and we are always happy reactions between the sample material and DTA crucibles, slip-on plates, to hear from you.

2 Table of Contents

Crucibles Sensors and Sample Carriers 38

Selection of Crucibles ��4 DSC 204 F1 Phoenix® Sensors, TG 209 F1 Iris®/Libra® and TG 209 F3 Tarsus® Sample Carriers ��40

DSC 204 F1 Phoenix®/DSC 200 F3 Maia®/DSC 3500 Sirius/ c-DTA® – More Than an Easy Calibration Routine ��42 DSC 214 Polyma ��6 DTA and DSC Sensors for the DSC 404 F1/F3 Pegasus® ��44 Standard Crucibles made of Aluminum ��7 TGA Sample Carriers and TGA-DTA Sensors for the Crucibles for General and Special Applications ��8 STA 449 F1/F3 Jupiter® ��46 Sealing Press, Sample Preparation and TGA-DTA and TGA-DSC Sensors for the Pressure-Tight Crucibles ��10 STA 449 F1/F3 Jupiter® ��48 Crucibles for Automatic Sample Changer (ASC) ��12 Radiation Shield for STA Systems ��50 Special Crucibles for Special Applications ��16 TGA and TGA-DSC Sensors for C Determination and p Operation with the Automatic Sample Changer (ASC) for the STA 449 F1/F3 Jupiter® ��52 TG 209 F1 Libra®/TG 209 F3 Tarsus® ��18 Different Sensor Types – The Right Sensor for Each Crucibles for General Applications ��19 Application ��54 Crucibles for Automatic Sample Changer (ASC) ��20 Tungsten for Highest Temperature Applications ��56 Applications ��23 Special Sample Carriers for Special Applications – OTS® ��58

Hanging Samples ��60 STA F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® ��24 Crucibles Made of Aluminum ��25 Calibration 62 DSC Crucibles for Measurements in a Pressure-Tight

Environment ��26 Calibration Materials �� 64 Large TGA Crucibles and Slip-On Plates ��27 Calibration Kits for DSC and DTA �� 65 Knudsen Cells (TGA); TGA and TGA-DTA Crucibles Calibration Kits for TGA and STA �� 68 Through to the Highest Temperature Range ��28 TGA-DTA, DSC and TGA-DSC Crucibles ��30 Chemical Behavior of Pt, Al2O3 and Crucibles for Automatic Sample Changer (ASC) ��32 Graphite Crucibles and Sensors 70 Applications – Special Crucibles for Large Samples,

Oxygen-Sensitive Alloys ��34 Material Compatibility – Sample in Crucible 72 Applications – Special Crucibles for High

Temperatures ��36 Recommendations for Cleaning Al2O3 and Pt Crucibles 74

3 Crucibles

Selection of Crucibles

Crucibles and Their Selection

Crucibles and their lids are made of such as nickel and zirconium have also materials resistant to high temperatures, been used. The type of crucible used usually porcelain or an inert metal. for thermoanalytical measurements Ceramics such as alumina, zirconia, can have a strong influence on the and especially magnesia will tolerate measurement results obtained. the highest temperatures. One of the Additionally, the crucible can also first metals used in crucible production influence the characteristics of the was platinum; more recently, metals instrument’s measuring cell.

4 Important Factors for Selection of Suitable DSC, TGA and STA Crucibles for Your Sample

The DSC crucible should have a flat in the programmed temperature bottom and be made of a material range; the melting point or fusion with a high thermal conductivity. This temperature must exceed the guarantees optimum heat transfer maximum application temperature to and low temperature gradients a sufficient degree. between the sample, crucible and sensor. The dimension, shape and specific heat of the crucible should be The crucible should be made of an optimized to achieve and/or maintain inert material in order to prevent the highest caloric sensitivity reactions with the sample in the and lowest time constant for the programmed temperature range. measuring system. Optimized Exceptions are crucibles for which parameters will result in sharp, a catalytic effect on the sample is well-defined and clearly separated desired (e.g., copper crucible for peaks. OIT tests, etc.). Crucibles should be reusable, The crucible should not exhibit any especially special ones for specific phase transitions or other effects applications.

Sample Material Crucible Volume Temperature Range Atmosphere CRUCIBLE SELECTION

Automatic Sample Changer Sample Compatibility Test Method

5 DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma Standard Aluminum Crucibles

Crucibles for the DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma

The following tables list the crucibles The premium Concavus pans have a for the low-temperature DSC systems unique geometry which features a DSC 204 F1 Phoenix®, DSC 200 F3 concave bottom. The pans are delivered Maia®, DSC 3500 Sirius and DSC 214 in the antistatic 3in1 Box. This elaborate Polyma. Many of these crucibles can packing prevents deformation of the also be used for the high-temperature pans, while allowing easy access of DSC and STA systems and can be found them and providing a fully functional in those tables as well. archiving system.

Please note that the temperatures For special applications such as boiling listed indicate the maximum point determination for volatile temperature ranges of the crucible substances or gypsum investigations, Al material but not of the DSC systems. lids with a laser-cut hole (50 μm) can be used. The lids can be cold-welded to the Some of the crucibles made of standard Al crucible. aluminum can be cold-welded with a sealing press. The standard Al crucibles Our high-pressure crucibles are capable and lids can be sealed to obtain a of withstanding a maximum of 100 bar volume of either 40 μl or 25 μl by of internal pressure. A single sealing simply reversing the lid. This ensures tool handles the job identically for all that samples of various shapes, such high-pressure crucible varieties. Each as pellets or fibers, can make optimum crucible comes with a seal. The gold contact with the crucible bottom. seals will be expended but can be ordered separately in order to continue using the crucible. The medium-pressure crucible withstands pressures up to 20 bar.

6 ® ® Standard Crucibles Made of Aluminum for the DSC 204 F1 Phoenix , DSC 200 F3 Maia , DSC 3500 Sirius and DSC 214 Polyma

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity) Range Volume

Al (99.5) Max. 600°C Crucible + lid ø 6 mm; 25/40 μl* Set of 100 pcs., cold weldable** 6.239.2-64.5.00 Al (99.5) Max. 600°C Crucible + lid ø 6 mm; 25/40 μl* Set of 500 pcs., cold weldable** 6.239.2-64.51.00 Al (99.5) Max. 600°C Crucible ø 6 mm; 25/40 μl* 100 pieces 6.239.2-64.5.01 Al (99.5) Max. 600°C Lid Set of 100 pcs. for 6.239.2-64.5.01 6.239.2-64.5.02 Crucible + lid with Al (99.5) Max. 600°C ø 6 mm; 40 μl Set of 100 pcs., cold weldable** 6.239.2-64.8.00 laser-cut hole (50 μm) Crucible + lid with Al (99.5) Max. 600°C ø 6 mm; 40 μl Set of 500 pcs., cold weldable** 6.239.2-64.81.00 laser-cut hole (50 μm) 96 Concavus pans Al (99.5) Max. 600°C ø 5 mm; 30/40 μl 3in1 Box (archiving system) DSC21400A66.010.00 and lids*** Al (99.5) Max. 600°C Concavus pan*** ø 5 mm; 30/40 μl 96 pieces including 3in1 Box NGB814672 Al (99.5) Max. 600°C Concavus lid*** Set of 96 pieces NGB814673 Al (99.5) Max. 600°C Crucible ø 6.7mm; 85 μl Set of 100 pieces NGB810405 Al (99.5) Max. 600°C Lid 100 pieces, for NGB810405 NGB810406

* Crucible volumes of either 25 μl or 40 μl can be achieved by simply reversing the lid. ** One and the same sealing press is capable of sealing all standard Al crucibles; order no. 6.240.10-80.0.00A. *** Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

Concavus pans with lids Crucibles with lids Al crucible with laser-cut Al lid

Al Lid with Laser-Cut Hole DSC /(mW/mg) ↓ exo 35 Evaporation of volatile substances usually starts before the boiling point of 30 the volatile is reached. This measurement shows that the 25 evaporation of water can be suppressed

20 crucible with 50µm hole in the lid by using a cold weldable aluminum lid crucible with pierced hole in the lid with a defined hole (ø 50 μm, green 15 curve). The comparison measurement

10 uses a lid with a punched hole. Here, evaporation already begins at slightly 5 above 60°C (blue curve). Cold weldable lids with laser-cut holes 0 Onset: 102.5 °C can also be used for gypsum 40 60 80 100 120 140 Temperature /°C applications. The separation of dihydrate

Using Al crucibles and lid with laser-cut hole (ø 50-μm hole) suppresses evaporation of solvents and other (DH) and half hydrate (HH) can be volatiles. Furthermore, these lids can be used for gypsum investigations. achieved.

7 DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma Crucibles for General and Special Applications

® ® Crucibles for General Applications – DSC 204 F1 Phoenix , DSC 200 F3 Maia , DSC 3500 Sirius and DSC 214 Polyma

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity) Range Volume

Al2O3 (99.7) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399972

Al2O3 (99.7) Max. 1700°C Lid For GB399972 GB399973 Fused silica Max. 1000°C Crucible ø 6.7 mm / 85 μl GB399974 Fused silica Max. 1000°C Lid For GB399974 GB399975 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399205 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 190 μl NGB801556 For GB399205 Pt/Rh (80/20) Max. 1700°C Lid GB399860 and NGB801556 Gold (99.9) Max. 900°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.3.00 Ampoules made of Duran glass Silver Max. 750°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.4.00 or fused silica are available.

Temp. /°C Influence of the Crucible on the DSC /(mW/mg) Flow /(ml/min) [1.4] [1.4] Oxidative-Induction Time (OIT) ↓ exo HDPE 250 280 0,4 The oxidative-induction time (OIT) can be determined in standard aluminum or 0,2 OIT Cu crucible OIT Al crucible 260 200 O.I.T.: 10,0 min O.I.T.: 32,8 min in open copper crucibles in accordance 0,0 with ASTM D3895. DSC 240 -0,2 150 This plot represents an OIT measure-

-0,4 220 ment of HDPE carried out in open 100 copper (red) and Al (black) crucible -0,6 Temperature respectively. It can clearly be seen that, 200 -0,8 under isothermal conditions, oxidation 50 Gas Flow blue: oxygen of HDPE begins approximately 23 min -1,0 green: nitrogen 180 olive: protective gas (nitrogen) earlier in the copper crucible than in the -1,2 0 Al crucible.

15 20 25 30 35 40 45 50 Time /min

Created with NETZSCH Proteus software Comparison of the oxidative-induction time in open copper and aluminum crucibles.

Special crucibles made of copper and aluminum for OIT tests

8 ® ® Special Crucibles for Special Applications – DSC 204 F1 Phoenix , DSC 200 F3 Maia , DSC 3500 Sirius and DSC 214 Polyma

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity) Range Volume For OIT measurements according to ASTM D3895 Cu Max. 600°C Crucible ø 6 mm / 25/40 μl 6.239.2-64.6.00 (Oxidative-Induction Time), Set of 25 Set of 100, not available for DSC 214 Polyma, after Duran glass Max. 600°C Ampoule 80 μl 6.240.1-93.2.00 sealing ampoule length ≈19 mm After sealing ampoule length Fused silica Max. 1000°C Ampoule 80 μl NGB815223 ≈ 19 mm For DSC 204 F1: Seal-off support for glass ampoules Auxiliary kit for glass Small welder with butane and oxygen gas bottles 6.240.10-93.1.00 ampoules Inner lid for measuring cell for use with glass ampoules Seal-off support for glass ampoules For DSC 200 F3 Small welder with butane and oxygen gas bottles Maia®: Auxiliary kit 6.240.20-93.1.00 Inner lid for measuring cell for use with glass ampoules for glass ampoules 100 ampoules Especially for determination of the OIT of lubricants and grease in accordance to ASTM D5483-5 and Solid For DSC 204 F1 Fat Index (SFI) in accordance Phoenix® with to ASTM D6186 τ-sensor and DSC Max. 600°C Crucible ø 6.7 mm / 85 μl Required accessories to obtain NGB810405 214 Polyma: OIT/SFI crucible design: Al (99.5) Sealing press 6.240.10-80.0.00A Stamping toolkit 6.240.10-84.0.00 Lid NGB810406

9 DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma Sealing Press, Sample Preparation and Pressure-Tight Crucibles

Sealing Press/Tools Sample Preparation

The sealing press (order no. For the sample preparation, we offer Kit for high-temperature range: 6.240.10-80.0.00A) can be equipped two kits for the low- and high- cutting board, scissors, hollow punch, with five toolkits for sealing and temperature range: scriber, glass-fiber brush, tweezers, stamping of different crucible types: spatula, scalpel, 5 scalpel blades, 5 Toolkit for Concavus pan: Kit for low-temperature range: single-edge blades, shaping tool, order no. 6.240.10-85.0.00 cutting board, scissors, hollow crucible holder, weighing support,

Toolkit for Al crucible: punch, scriber, glass-fiber brush, crucible box with 4 Al2O3 crucibles, order no. 6.240.10-81.0.00 tweezers, spatula, scalpel, 5 scalpel post-it, manual Toolkit for low-pressure Al crucible: blades, 5 single-edge blades, ball order no. DSC404F1A99.000-00 order no. 6.240.10-82.0.00 pen, post-it, space for business card Toolkit for sealing of medium- of the NETZSCH contact, manual pressure crucibles: order no. order no. 6.240.12-99.0.00 6.240.10-83.0.00 Stamping toolkit 6.240.10-84.0.00 for SFI crucible NGB810405

Sealing tool for the high-pressure crucibles, order no. 6.239.2-92.4.00

SampleCutter tool for cutting and creating of plane-non-metallic samples (e.g., polymer granulates), order no. NGB814695 10 spare blades for SampleCutter, order no. NGB 814821

Crucibles Made of Aluminum – Low-Pressure

Material Temperature Dimension/Volume/ Consisting of Remarks Order Number (Purity) Range Pressure Set of 100 pieces, Al (99.5) Max. 600°C Crucible + Lid ø 6 mm / 35 μl; 3 bar 6.240.10-65.1.00 cold weldable Set of 500 pieces, Al (99.5) Max. 600°C Crucible + Lid ø 6 mm / 35 μl; 3 bar 6.240.10-65.11.00 cold weldable Al (99.5) Max. 600°C Crucible ø 6 mm / 35 μl; 3 bar 100 pieces NGB810419 Al (99.5) Max. 600°C Lid For crucibles of ø 6 mm 100 pieces NGB810420

10 Medium- and High-Pressure Crucibles

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity) Range Volume/Pressure CrNi steel Crucible + lid + Max. 250°C 120 μl; 20 bar Set of 25 pieces 6.240.1-68.1.00 (AISI 304) elastomer seal O-ring seal Max. 250°C O-ring Max. 20 bar Elastomer seal: PCTFE NGB801765 Crucible + lid, 1 crucible + CrNi steel hexagonal, ø 6 mm, 27 μl, Max. 500°C 5 Au sealing disks 6.239.2-92.3.00 (AISI 316L) gold-plated max. 100 bar (sealing press 6.239.2-92.4) surface, reusable Crucible + lid, 10 crucibles + CrNi steel hexagonal, ø 6 mm, 27 μl, Max. 500°C 50 Au sealing disks 6.239.2-92.31.00 (AISI 316L) gold-plated max. 100 bar (sealing press 6.239.2-92.4) surface, reusable Crucible + lid, 1 crucible + CrNi steel hexagonal, ø 6 mm, 100 μl, Max. 500°C 5 Au sealing disks 6.239.2-92.8.00 (AISI 316L) gold-plated max. 100 bar (sealing press 6.239.2-92.4) surface, reusable Crucible + lid, 1 crucible + CrNi steel ø 6 mm, 27 μl, Max. 500°C hexagonal, 5 Au sealing disks 6.239.2-93.3.00 (AISI 316L) max. 100 bar reusable (sealing press 6.239.2-92.4) Crucible + lid, 10 crucibles + CrNi steel ø 6 mm, 27 μl, Max. 500°C hexagonal, 50 Au sealing disks 6.239.2-93.31.00 (AISI 316L) max. 100 bar reusable (sealing press 6.239.2-92.4) Crucible + lid, 1 crucible + CrNi steel ø 6 mm, 100 μl, Max. 500°C hexagonal, 5 Au sealing disks 6.239.2-93.4.00 (AISI 316L) max. 100 bar reusable (sealing press 6.239.2-92.4) Crucible + lid, 1 crucible + CrNi steel ø 6 mm, 100 μl, Max. 500°C hexagonal, 5 Au sealing disks 6.239.2-93.41.00 (AISI 316L) max. 100 bar reusable (sealing press 6.239.2-92.4) Crucible + lid, 1 crucible + Titanium ø 6 mm, 27 μl, Max. 500°C hexagonal, 5 Au sealing disks 6.239.2-92.6.00 (Grade 4) max. 100 bar reusable (sealing press 6.239.2-92.4) Crucible + lid, 1 crucible + Titanium ø 6 mm, 100 μl, Max. 500°C hexagonal, 5 Au sealing disks 6.239.2-92.9.00 (Grade 4) max. 100 bar reusable (sealing press 6.239.2-92.4) Au seals Max. 500°C For all high-pressure autoclaves, alloy: Au 58.5%, Ag 26%, Cu 15.5% 6.240.1-91.1.00 (Au 585) For crucibles: 6.239.2-92.3.00, -92.31.00, -92.6.00, -92.8.00, Sealing press 6.239.2-92.4.00 -92.9.00, -93.3.00, -93.31.00, -93.4.00, -93.41.00

Medium-pressure crucible (right) and high-pressure crucible (left)

11 DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma Crucibles for Operation with the Automatic Sample Changer (ASC)

® Crucibles for DSC 200 F3 Maia , DSC 3500 Sirius and DSC 214 Polyma in ASC Operation

ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel DSC 200 F3 Standard Order Number Lid Large Crucibles (TG 209 F3) Crucibles Al (99.5), 30/40 μl (Concavus pan) x* x x DSC21400A66.010.00 Crucible with welded lid x* x x Al (99.5), 25/40 μl x x x 6.239.2-64.5.00 Crucible with welded lid x x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.51.00 Crucible with welded lid x x x Al (99.5), 25/40 μl x x x 6.239.2-64.8.00 Crucible and lid with laser-cut-hole x x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.81.00 Crucible and lid with laser-cut-hole x x x Al (99.5), low-pressure, 35 μl x x x 6.240.10-65.1.00 Crucible with welded lid x x x CrNi steel (AISI 304), medium-pressure, x x Only for manual operation 6.240.1-68.1.00 120 μl, 20 bar Crucible with lid x x Copper, 25 μl x x Only for manual operation 6.239.2-64.6.00 CrNi steel (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.3.00 27 μl, gold-plated, 100 bar CrNi steel (AISI 316L), high-pressure, 27 μl, x x Only for manual operation 6.239.2-93.3.00 100 bar CrNi (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.8.00 100 μl, gold-plated, 100 bar CrNi (AISI 316L), high-pressure, 100 μl, x x Only for manual operation 6.239.2-93.4.00 100 bar Ti (Grade 4), high-pressure, 27 μl, 100 bar x x Only for manual operation 6.239.2-92.6.00 Ti (Grade 4), high-pressure, 100 μl, 100 bar x x Only for manual operation 6.239.2-92.9.00

12 ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel DSC 200 F3 Standard Order Number Lid Large Crucibles (TG 209 F3) Crucibles Pt/Rh (80/20), ø 6.8 x 6 mm, 190 μl x x Only for manual operation NGB801556 Crucible with lid (note: lid order no.) - x GB399860 Al (99.5), ø 6.7 mm, 85 μl x x Only for manual operation NGB810405 Crucible with lid (note: lid order no.) - x NGB810406 Graphite, ø 6.8mm, 85 μl x x Only for manual operation GB399956 Crucible with lid (note: lid order no.) - x GB399957 Gold (99.9), ø 6.8 mm, 85 μl, x x Only for manual operation 6.225.6-93.3.00 Crucible with lid (99.9) - x Silver, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.4.00 Crucible with lid - x

ZrO2, ø 6.8mm, 85 μl x x Only for manual operation GB397053 Crucible with lid (note: lid order no.) - x GB397052

Y2O3, ø 6.8mm, 85 μl x x Only for manual operation NGB812636 Crucible with lid (note: lid order no.) x x NGB812635 MgO, ø 6.8mm, 85 μl x x Only for manual operation NGB812639 Crucible with lid (note: lid order no.) x x NGB812637

Al2O3 (99.7), ø 8 x 8 mm, 300 μl x - x NGB803698 Crucible with lid (note: lid order no.) - - x NGB808209

Pt/Rh/Al2O3 system with lid - x Only for manual operation 6.225.6-93.2.00 * Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

Concavus pans with lids, 30 μl or 40 μl Al crucibles with lids, 25 μl or 40 μl

13 DSC 204 F1 Phoenix® Crucibles for Operation with the Automatic Sample Changer (ASC)

Crucibles for DSC 204 F1 Phoenix® (TG 209 F1 Libra®) in ASC Operation, possible for μ- and τ-sensor

ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel DSC 204 F1 Standard Order Number Lid Large Crucibles (TG 209 F1) Crucibles Al (99.5), 30/40 μl (Concavus pan) x* x x DSC21400A66.010.00 Crucible with welded lid x* x x Al (99.5), 25/40 μl x x x 6.239.2-64.5.00 Crucible with welded lid x x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.51.00 Crucible with welded lid x x x Al (99.5), 25/40 μl x x x 6.239.2-64.8.00 Crucible and lid with laser-cut-hole x x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.81.00 Crucible and lid with laser-cut-hole x x x Al (99.5), low-pressure, 35 μl x x x 6.240.10-65.1.00 Crucible with welded lid x x x CrNi steel (AISI 304), - x Only for manual operation 6.240.1-68.1.00 medium-pressure, 120 μl, 20 bar Crucible with lid - x Copper, 25 μl x x Only for manual operation 6.239.2-64.6.00 CrNi steel (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.3.00 27 μl, gold-plated, 100 bar CrNi steel (AISI 316L), high-pressure, 27 μl, x x Only for manual operation 6.239.2-93.3.00 100 bar CrNi (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.8.00 100 μl, gold-plated, 100 bar CrNi (AISI 316L), high-pressure, 100 μl, x x Only for manual operation 6.239.2-93.4.00 100 bar Ti (Grade 4), high-pressure, 27 μl, 100 bar x x Only for manual operation 6.239.2-92.6.00 Ti (Grade 4), high-pressure, 100 μl, 100 bar x x Only for manual operation 6.239.2-92.9.00

Concavus pans in a 3in1 Box

14 ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel DSC 204 F1 Standard Order Number Lid Large Crucibles (TG 209 F1) Crucibles

Al2O3 (99.7), ø 6.8 mm, 85 μl x x Only for manual operation GB399972 Crucible with lid (note: lid order no.) x x GB399973 Fused silica, ø 6.8 mm, 85 μl x x Only for manual operation GB399974 Crucible with lid (note: lid order no.) - x GB399975 Pt/Rh (80/20), ø 6.8 mm, 85 μl x x Only for manual operation GB399205 Crucible with lid (note: lid order no.) - x GB399860 Pt/Rh (80/20), ø 6.8 mm, 85 μl x x Only for manual operation NGB801556 Crucible with lid (note: lid order no.) - x GB399860 Al (99.5), ø 6.7 mm, 85 μl x x Only for manual operation NGB810405 Crucible with lid (note: lid order no.) - x NGB810406 Graphite, ø 6.8 mm, 85 μl x x Only for manual operation GB399956 Crucible with lid - x GB399957 Gold, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.3.00 Crucible with lid - x Silver, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.4.00 Crucible with lid (note: lid order no.) - x

ZrO2, ø 6.8 mm, 85 μl x x Only for manual operation GB397053 Crucible with lid (note: lid order no.) - x GB397052

Y2O3, ø 6.8 mm, 85 μl x x Only for manual operation NGB812636 Crucible with lid (note: lid order no.) x x NGB812635 MgO, ø 6.8 mm, 85 μl x x Only for manual operation NGB812639 Crucible with lid (note: lid order no.) x x NGB812637

Al2O3 (99.7), ø 8 x 8 mm, 300 μl - - x NGB803698 Crucible with lid (note: lid order no.) - - x NGB808209

Pt/Rh/Al2O3 system with lid - x Only for manual operation 6.225.6-93.2.00 * Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

15 DSC 204 F1 Phoenix®, DSC 200 F3 Maia®, DSC 3500 Sirius, DSC 214 Polyma Special Crucibles for Special Applications

Internal Pressure Capabilities of Sealed Al, Fine Steel, and CrNi Steel Crucibles

A material’s potential reaction and/or type of investigation being conducted (e.g., denaturation of starch, curing of phenolic resin), may warrant the use of crucibles capable of certain levels of internal pressure. The plot shows four measurements on water, of approximately 30 µl each, in different crucible types: Al standard, Al low-pressure (max. 3 bar), fine steel medium-pressure, and CrNi steel autoclaves. It can be observed that the standard Al crucible starts to leak at approximately 125°C, while the low-pressure Al pan opens above 150°C when water is trapped inside. The medium- pressure crucibles (20 bar) withstand the inner pressure increase up to their maximum temperature. The high-pressure crucibles begin to leak around 400°C. Comparison of measurements done in crucibles capable of withstanding various levels of internal pressure

Melting and Boiling Point Determination for a Polycyclic Aromatic Hydrocarbon

Polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, are formed during TG /% DSC /(mW/mg) natural and anthropogenic processes like 230.2 °C ↓ exo 4.0 volcanic eruptions, forest fires, etc. They 100 3.5 are released into the atmosphere and, due 80 Sample: Naphthalene to their hydrophobicity, accumulate in soil 3.0 60 and may enter into the food chain. 2.5 -100.01 % This measurement was designed to 91.7 °C 2.0 determine the melting and boiling point 40 1.5 of naphthalene. A sealed Al crucible 20 Area: 129 J/g Area: 267 J/g with a 50-μm laser-cut hole was used. Onset: 81.4 °C Onset: 217.8 °C 1.0 0 At an extrapolated onset temperature 0.5 of 81°C, melting occurred with an 0.0 enthalpy of 129 J/g. A mass-loss step of -20 50 100 150 200 250 100% took place between 150°C and Temperature /°C 230°C; this reflects evaporation of the sample. This effect was accompanied STA 449 F3 Jupiter® measurement using the by an endothermic DSC peak with an TGA-DSC sensor for determination of the melting and boiling points of naphthalene (sample mass enthalpy of 267 J/g and an extrapolated 22.66 mg, heating rate 10 K/min, 70 ml/min onset of 218°C. The latter reflects the nitrogen atmosphere) boiling point of naphthalene. These results correspond to the nominal values. Al crucible with laser-cut Al lid

16 Oxidative-Induction Time (OIT) and Solid Fat Index (SFI) Tests on Lubricating Greases

Grease and wax samples can be Pressure /Bar prepared with more consistent surface DSC /(mW/mg) Temp. /°C [6.4] areas when using SFI crucibles instead ↓ exo 35Bar 35 of flat-bottom crucibles. The results 10 180 show an increased reproducibility. In this example, an OIT measurement 8 30 160 on grease was carried out with the DSC 6 sample grease 25 140 204 HP Phoenix® with a standard Al

4 120 crucible and the SFI crucible under an 20 oxygen pressure of 35 bar as per ASTM SFI Al crucible standard Al crucible 2 OIT: 46.4 min OIT: 64.6 min 100 D5483-5. The difference in the OIT is 15 clearly visible. The oxidative-induction 0 80 time of the grease in the SFI crucible is 10 60 approximately 21 min shorter than the -2 5 static air, no pressure 40 one in the standard Al crucible. This -4 effect results from the more consistent Oxygen, 35 bar 0 20 sample surface area made possible by 0 10 20 30 40 50 60 70 80 Time /min use of the SFI crucible. Oxidation stability in two different Al crucibles

SFI crucible for an OIT test of lubricants and greases on special stamping tool for sealing press 6.240.10-80.0.00A

17 TG 209 F1 Libra® and TG 209 F3 Tarsus® Crucibles for General Applications

Crucibles for the TG 209 F1 Libra® and TG 209 F3 Tarsus®

The TG 209 F1 Libra® and TG 209 A large variety of crucibles is F3 Tarsus® both offer sample carriers available to cover the temperature for regular and large sample masses, range for different materials, guaranteeing broad applications in including large crucibles required the temperature range from room for substances with a high sample temperature to 1000°C and 1100°C, mass and low density (e.g., foams, respectively. aerogels, etc.).

18 ® ® Crucibles for the TG 209 F1 Libra and TG 209 F3 Tarsus Crucibles for General Applications – TG 209 F1 Libra® and TG 209 F3 Tarsus®

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume

Al2O3 (99.7) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399972

Al2O3 (99.7) Max. 1700°C Lid For GB399972 GB399973 Fused silica Max. 1000°C Crucible ø 6.7 mm / 85 μl GB399974 Fused silica Max. 1000°C Lid For GB399974 GB399975 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399205 Pt/Rh (80/20) Max. 1700°C Lid For GB399205 and NGB801556 GB399860 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 190 μl NGB801556 Al (99.5) Max. 610°C Crucible ø 6.7 mm / 85 μl Set of 100 pieces NGB810405 Al (99.5) Max. 610°C Lid For NGB810405 NGB810406 Gold (99.9) Max. 900°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.3.00 Silver Max. 750°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.4.00

ZrO2 Max. 2000°C Crucible 85 μl CaO-stabilized GB397053

ZrO2 Max. 2000°C Lid For GB397053 GB397052 Graphite Max. 2200°C Crucible 85 μl GB399956 Graphite Max. 2200°C Lid For GB399956 GB399957 ø 9 mm, height 7 mm, Sample holder for large samples Al O (99.8) Max. 1700°C Crucible NGB800453 2 3 volume 350 μl required

Al2O3 (99.8) Max. 1700°C Lid NGB800454 ø 8 mm, height 8 mm, Sample holder for large samples Al O (99.7) Max. 1700°C Crucible NGB803698 2 3 volume 300 μl required, ASC-compatible

Al2O3 (99.7) Max. 1700°C Lid For crucible NGB803698 NGB808209

Large crucible made of Al2O3, volume 350 ul Large crucible made of Al2O3, volume 300 ul Crucibles made of Pt

19 TG 209 F1 Libra® and TG 209 F3 Tarsus® Crucibles for Operation with the Automatic Sample Changer (ASC)

Crucibles for TG 209 F1 Libra® (& DSC 204 F1 Phoenix®) in ASC Operation

ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel TG 209 F1 Standard Order Number Lid Large Crucibles (DSC 204 F1) Crucibles Al (99.5), 30/40 μl (Concavus pan) x* x x DSC21400A66.010.00 Crucible with welded lid x x x Al (99.5), 25/40 μl x x x 6.239.2-64.5.00 Crucible with welded lid x x x Al (99.5), 25/40 μl x x x 6.239.2-64.8.00 Crucible and lid with laser-cut-hole x x x Al (99.5), low-pressure, 35 μl x x x 6.240.10-65.1.00 Crucible with welded lid x x x CrNi steel (AISI 304), - x Only for manual operation 6.240.1-68.1.00 medium-pressure, 120 μl, 20 bar Crucible with lid - x Copper, 25 μl x x Only for manual operation 6.239.2-64.6.00 CrNi steel (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.3.00 27 μl, gold-plated, 100 bar CrNi steel (AISI 316L), high-pressure, 27 μl, x x Only for manual operation 6.239.2-93.3.00 100 bar CrNi (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.8.00 100 μl, gold-plated, 100 bar CrNi (AISI 316L), high-pressure, 100 μl, x x Only for manual operation 6.239.2-93.4.00 100 bar Ti (Grade 4), high-pressure, 27 μl, 100 bar x x Only for manual operation 6.239.2-92.6.00 Ti (Grade 4), high-pressure, 100 μl, 100 bar x x Only for manual operation 6.239.2-92.9.00

Al2O3 (99.7), 6.8 mm, 85 μl x x Only for manual operation GB399972 Crucible with lid (note: lid order no.) - x GB399973 Fused silica, ø 6.8 mm, 85 μl x x Only for manual operation GB399974 Crucible with lid (note: lid order no.) - x GB399975

20 ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel TG 209 F1 Standard Order Number Lid Large Crucibles (DSC 204 F1) Crucibles

Pt/Rh (80/20), ø 6.8 mm, 85 μl x x Only for manual operation GB399205 Crucible with lid (note: lid order no.) - x GB399860 Pt/Rh (80/20), ø 6.8 x 6 mm, 190 μl x x Only for manual operation NGB801556 Crucible with lid (note: lid order no.) - x GB399860 Al (99.5), ø 6.7 mm, 85 μl x x Only for manual operation NGB810405 Crucible with lid (note: lid order no.) - x NGB810406 Graphite, ø 6.8 mm, 85 μl x x Only for manual operation GB399956 Crucible with lid (note: lid order no.) - x GB399957 Gold, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.3.00 Crucible with lid - x Silver, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.4.00 Crucible with lid - x

ZrO2, ø 6.8 mm, 85 μl x x Only for manual operation GB397053 Crucible with lid (note: lid order no.) - x GB397052

Y2O3, ø 6.8 mm, 85 μl x x Only for manual operation NGB812636 Crucible with lid (note: lid order no.) x x NGB812635 MgO, ø 6.8 mm, 85 μl x x Only for manual operation NGB812639 Crucible with lid (note: lid order no.) x x NGB812637

Al2O3 (99.7), ø 8 x 8 mm, 300 μl x - x NGB803698 Crucible with lid (note: lid order no.) - - x NGB808209

Pt/Rh/Al2O3 system with lid - x Only for manual operation 6.225.6-93.2.00

* Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

21 TG 209 F1 Libra® and TG 209 F3 Tarsus® Crucibles for Operation with the Automatic Sample Changer – Applications

® ® Crucibles for TG 209 F3 Tarsus (& DSC 200 F3 Maia , DSC 3500 Sirius and DSC 214 Polyma) in ASC Operation

ASC Gripper Carousel Crucible Material (Purity/%), Volume Carousel TG 209 F3 Standard Order Number Lid Large Crucibles (DSC 200 F3) Crucibles Al (99.5), 30/40 μl (Concavus pan) x* x x DSC21400A66.010.00 Crucible with welded lid x x x

Al2O3 (99.7), ø 6.8 mm, 85 μl x x Only for manual operation GB399972 Crucible with lid (note: lid order no.) x x GB399973 Fused silica, ø 6.8 mm, 85 μl x x Only for manual operation GB399974 Crucible with lid (note: lid order no.) - x GB399975 Pt/Rh (80/20), ø 6.8 mm, 85 μl x x Only for manual operation GB399205 Crucible with lid (note: lid order no.) - x GB399860 Pt/Rh (80/20), ø 6.8 x 6 mm, 190 μl x x Only for manual operation NGB801556 Crucible with lid (note: lid order no.) - x GB399860 Al (99.5), ø 6.7 mm, 85 μl x x Only for manual operation NGB810405 Crucible with lid (note: lid order no.) - x NGB810406 Graphite, ø 6.8mm, 85 μl x x Only for manual operation GB399956 Crucible with lid (note: lid order no.) - x GB399957 Gold (99.9), ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.3.00 Crucible with lid (99.9) - x Silver, ø 6.8 mm, 85 μl x x Only for manual operation 6.225.6-93.4.00 Crucible with lid - x

ZrO2, ø 6.8mm, 85 μl x x Only for manual operation GB397053 Crucible with lid (note: lid order no.) - x GB397052

Al2O3 (99.7), ø 8 x 8 mm, 300 μl x - x NGB803698 Crucible with lid (note: lid order no.) - - x NGB808209

Pt/Rh/Al2O3 system with lid - x Only for manual operation 6.225.6-93.2.00 * Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

Please note: Other crucibles suitable for ASC operation are listed in the ASC table for the DSC 200 F3 Maia®, DSC 3500 Sirius and DSC 214 Polyma, see page 12

22 c-DTA® for Polymer Identification TG/% c-DTA® /K exo 2.5 HD-PE, PP and PA 6 exhibit very similar 100 decomposition behavior with regard HD-PE 2.0 PP to temperature and residual mass, 80 PA6 1.5 which makes it difficult to distinguish between them. However, when using 60 165.9°C 1.0 the TGA sensor for c-DTA® calibration in 142.0°C 224.5°C 0.5 40 combination with a platinum crucible, 0.0 the characteristic melting peaks of 20 Onset*: 119.9°C Onset*: 207.2°C these components can be monitored – Onset*: 151.1°C -0.5 even in a TGA system. The melting 0 -1.0 peak detected at 142°C can be clearly Residual Mass: 0.5 % (600.0°C) Residual Mass: 0.2 % (600.0°C) ascribed to HD-PE; the peak at 166°C, -20 -1.5 Residual Mass: 0.0 % (600.0°C) to PP; and the peak at 225°C, to PA 6. 100 200 300 400 500 600 Temperature/°C

The measurements were carried out using approximately 10 mg of the rubber mixture in a platinum crucible under a nitrogen atmosphere.

Precise Determination of the Temp./°C Plasticizer Content of a Tire Mixture TG/% DTG/(%/min)

2 900 The plasticizer content can be

vacuum refill with oxygen 800 determined precisely by carrying out a 100 1 -20.04% nitrogen TGA measurement under vacuum prior 700 0 to the decomposition of the rubber 80 -1 600 mixture. Because the boiling point is

-2 500 depressed under vacuum, the release 152.1°C 342.0°C -42.86% of the plasticizer at 152°C is clearly 60 rubber 647.7°C -3 400 volatiles compound 1 separated from the decomposition of combustion of carbon black -4 300 the rubber – which consists of two 40 compound 1 -9.08% -5 200 compounds, as indicated by the DTG 429.0°C rubber compound 2 ash content -6 100 peaks at 342°C and 429°C. After 20 Residual Mass: 28.03% (102.5 min) the decomposition under vacuum, at 0 20 40 60 80 100 600°C, nitrogen is filled into the TGA Time/min system. After 20 min stabilization

This measurement was performed in the TG F1 Libra®, using a 10-mg time, the atmosphere is changed to sample mass in an Al2O3 crucible. oxygen and the measurement proceeds at a linear heating rate (10 K/min). Under an oxygen atmosphere, carbon black immediately combusts to 9%. The residue in the crucible is the ash content, which was determined here to be 28%.

23 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® Crucibles Made of Aluminum

Crucibles for the STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus®

What sets the STA 449 F1/F3 Jupiter® are also available in different materials and DSC 404 F1/F3 Pegasus® systems and dimensions. apart is not only their flexibility in furnaces and sensors but also the huge For inhomogeneous samples and those variety of possible crucibles. For the with an extremely low density, special broad temperature range from -150°C TGA sample holders and large crucibles to 2400°C, the crucible materials vary are available. The automatic sample from aluminum to magnesium oxide changer (ASC) with its gripper and and tungsten to zirconium oxide. carousel allows for the use of nearly any crucible type including specialties such Besides DSC and TGA (for STA) as low-, medium- and high-pressure crucibles, plates and net-shaped plates crucibles.

24 Crucibles Made of Aluminum for the STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus®

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume Set of 96, 3in1 Box, Al (99.5) Max. 600°C Concavus pan* + lid ø 5 mm / 30/40 μl DSC21400A66.010.00 cold weldable** Al (99.5) Max. 600°C Concavus pan* ø 5 mm / 30/40 μl 3in1 Box, 96 pieces NGB814672 Al (99.5) Max. 600°C Concavus lid 96 pieces NGB814673 Al (99.5) Max. 600°C Crucible + lid ø 6 mm / 25/40 μl Set of 100, cold weldable** 6.239.2-64.5.00 Al (99.5) Max. 600°C Crucible + lid ø 6 mm / 25/40 μl Set of 500, cold weldable** 6.239.2-64.51.00 Crucible + punched lid Al (99.5) Max. 600°C ø 6 mm / 40 μl Set of 100, cold weldable** 6.239.2-64.8.00 (0.05 mm) Crucible + punched lid Al (99.5) Max. 600°C ø 6 mm / 40 μl Set of 500, cold weldable** 6.239.2-64.81.00 (0.05 mm) Set of 100 pieces, Al (99.5) Max. 600°C Crucible ø 6.7 mm /85 μl NGB810405 non-weldable Set of 100 pieces, for Al (99.5) Max. 600°C Lid NGB810406 NGB810405 * Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of ASC gripper. ** Please note: One and the same sealing press is capable of sealing all the Al crucibles, order no. 6.240.10-80.0.00A, see optional toolkits, page 12

Concavus pans in the antistatic 3in1 Box

Low-Pressure Crucibles Made of Aluminum for TGA-DSC Sensors of the STA 449 F1/F3 Jupiter®1 and DSC Sensors of the DSC 404 F1/F3 Pegasus®2

Material Temperature Dimension/Volume/ Consisting of Remarks Order Number (Purity/%) Range Pressure Set of 100 pieces, cold Al (99.5) Max. 600°C Crucible + lid ø 6 mm / 35 μl; 3 bar 6.240.10-65.1.00 weldable Set of 500 pieces, cold Al (99.5) Max. 600°C Crucible + lid ø 6 mm / 35 μl; 3 bar 6.240.10-65.11.00 weldable Al (99.5) Max. 600°C Crucible ø 6 mm / 35 μl; 3 bar 100 pieces 6.240.10-65.1.01 Al (99.5) Max. 600°C Lid For crucibles of ø 6 mm 100 pieces 6.240.10-65.1.02

1 STA 449 F1/F3 Jupiter® sensors: HTP40000AXX.000-00 (XX = 78, 77, 73, 74, 79 or 63) 2 DSC 404 F1/F3 Pegasus® sensors: DSC404F1AXX.000-00 (XX = 78, 77, 73, 74, 79 or 75)

25 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® DSC Crucibles for Measurements in a Pressure-Tight Environment, Large TGA Crucibles and Slip-On Plates

Medium- and High-Pressure Crucibles for TGA-DSC Sensors (HTP 40000A69/70/71/72.000-00) of the STA 449 F1/F3 Jupiter® and DSC sensors of the DSC 404 F1/F3 Pegasus®

Temperature Dimension/ Material Consisting of Remarks Order Number Range Volume/Pressure

CrNi steel Max. 250°C Crucible + lid + seal 120 μl; 20 bar Set of 25 pieces 6.240.1-68.1.00 (AISI 304)

O-ring seal Max. 250°C O-ring Max. 20 bar Elastomer seal: PCTFE NGB801765

Crucible + lid, CrNi steel ø 6 mm, 27 μl, 1 crucible + 5 Au sealing Max. 500°C hexagonal, gold-plated 6.239.2-92.3.00 (AISI 316L) max. 100 bar disks (sealing press 6.239.2-92.4) surface, reusable Crucible + lid, hexago- CrNi steel ø 6 mm, 27 μl, 10 crucible + 50 Au sealing Max. 500°C nal, gold-plated 6.239.2-92.31.00 (AISI 316L) max. 100 bar disks (sealing press 6.239.2-92.4) surface, reusable CrNi steel Crucible + lid, ø 6 mm, 27 μl, 1 crucible + 5 Au sealing Max. 500°C 6.239.2-93.3.00 (AISI 316L) hexagonal, reusable max. 100 bar disks (sealing press 6.239.2-92.4) CrNi steel Crucible + lid, ø 6 mm, 27 μl, 10 crucible + 50 Au sealing Max. 500°C 6.239.2-93.31.00 (AISI 316L) hexagonal, reusable max. 100 bar disks (sealing press 6.239.2-92.4) CrNi steel Crucible + lid, ø 6mm, 100 μl, 1 crucible + 5 Au sealing Max. 500°C 6.239.2-93.4.00 (AISI 316L) hexagonal, reusable max. 100 bar disks (sealing press 6.239.2-92.4) Crucible + lid, hexago- CrNi steel ø 6mm, 100 μl, 1 crucible + 5 Au sealing Max. 500°C nal, gold-plated 6.239.2-92.8.00 (AISI 316L) max. 100 bar disks (sealing press 6.239.2-92.4) surface, reusable Titanium Crucible + lid, ø 6 mm, 27 μl, 1 crucible + 5 Au sealing Max. 500°C 6.239.2-92.6.00 (Grade 4) hexagonal, reusable max. 100 bar disks (sealing press 6.239.2-92.4) Titanium Crucible + lid, hexago- ø 6mm, 100 μl, 1 crucible + 5 Au sealing Max. 500°C 6.239.2-92.9.00 (Grade 4) nal, reusable max. 100 bar disks (sealing press 6.239.2-92.4) Au seals Max. 500°C For all high-pressure autoclaves, alloy: Au 58.5%, Ag 26%, Cu 15.5% 6.240.1-91.1.00 (Au585) For crucibles: 6.239.2-92.3.00, -92.31.00, -92.6.00, -92.8.00, Sealing press 6.239.2-92.4.00 -92.9.00, -93.3.00, -93.31.00, -93.4.00, -93.41.00

Sealing tool for the high-pressure Medium-pressure crucible (right) and crucibles, order no. 6.239.2-92.4.00 high-pressure crucible (left)

26 Crucibles for TGA Sample Carrier (HTP40000A58.000-00) of the STA 449 F1/F3 Jupiter®

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume

Al2O3 (99.7) Max. 1700°C Slip-on plate, flat ø 10 mm GB343550

Al2O3 (99.7) Max. 1700°C Slip-on plate ø 17 mm GB445240

Al2O3 (99.7) Max. 1700°C Crucible 0.9 ml GB445215

Al2O3 (99.7) Max. 1700°C Lid For GB445215 GB445216

Al2O3 (99.7) Max. 1700°C Crucible 3.4 ml GB445213 Lid without hole, Al O (99.7) Max. 1700°C Lid GB445214 2 3 for GB445213

Al2O3 (99.7) Max. 1700°C Crucible 5.0 ml NGB809163 Lid without hole, Al O (99.7) Max. 1700°C Lid NGB814785 2 3 for NGB809163 For sample dimension: Al O (99.7) Max. 1700°C Crucible NGB811934 2 3 ø 15 mm; hight 25 mm

ø 18 mm; øinner14.5 mm; total height 14.5 mm; For glove box Al O (99.7) Max. 1700°C Crucible NGB811194 2 3 filling height 3 mm; applications volume 0.53 ml Repository Crucible repository with handling tool, for glove box crucible NGB811194 HTP40000A91.000-00 Pt/Ir (90/10) Max. 1600°C Net-shaped slip-on plate ø 17 mm (100 meshes/cm2) GB398029 Pt/Ir (90/10) Max. 1600°C Net-shaped slip-on plate ø 17 mm (225 meshes/cm2) GB398030 Pt/Ir (90/10) Max. 1600°C Slip-on plate ø 10 mm GB348834 Pt/Ir (90/10) Max. 1600°C Slip-on plate ø 17 mm GB348835

Al2O3 slip-on plates (ø 10 mm, 17 mm) Al2O3 crucible for glove box applications

Al2O3 crucibles with different volumes Pt/Ir net-shaped slip-on plates (0.9 ml, 3.4 ml, 5 ml) (ø 17 mm, 100/225 meshes/cm2)

27 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® Knudsen Cells (TGA), TGA and TGA-DTA Crucibles Through to the Highest Temperature Range

Crucible for TGA Sample Carrier (HTP40000A64.000-00/-010.00)

Temperature Material Sample Chamber Dimension Remarks Order Number Range Only for TGA-sample carrier Fused Silica Max. 1100°C 3.4 ml NGB811507 HTP40000A64.000-00

Large crucible made of fused silica

Crucibles for TGA Sample Carrier (HTP40000A58.000-00) of the STA 449 F1 Jupiter® with Turbo Pump – Knudsen Cells

Material Temperature Sample Chamber Dimension Remarks Order Number (Purity/%) Range ø 12 mm x 3.7 mm high; orifice ZrO Max. 2000°C Crucible + lid 6.226.1-69.5.00 2 ø 2.896 mm (optically dimensioned) ø 12 mm x 3.7 mm high; orifice Al O (99.7) Max. 1700°C Crucible + lid 6.226.1-67.1.00 2 3 ø 2.896 mm (optically dimensioned) Crucible + lid;

Al2O3 (99.7) Max. 1700°C Outlet ø 0.3 mm (optically dimensioned) also for carrier: 6.226.1-69.1.00 6.226.1-58.0.00+S

Al2O3 (99.7) Max. 1700°C Outlet ø 0.1 mm (optically dimensioned) Crucible + lid 6.226.1-69.2.00 ø 12 mm x 3.7 mm high; orifice Molybdenum Max. 2000°C Crucible + lid 6.226.1-69.4.00 ø 2.896 mm (optically dimensioned) MgO Max. 1500°C Outlet ø 0.3 mm (optically dimensioned) Crucible + lid* 6.226.1-68.1.00

* depending on the atmosphere, the cell can potentially withstand 1650°C for short periods

Knudsen cells with different dimensions and orifice diameters

Crucibles for TGA Sample Carrier (HTP40000A52.000-00) of the STA 449 F1/F3 Jupiter®

Material Temp. Range Consisting of Dimension/Volume Remarks Order Number

Tungsten Max. 2400°C Crucible 0.3 ml NGB809001 Graphite Max. 2200°C Crucible 0.3 ml GB445333

Tungsten crucible (right) and graphite crucible (left)

28 Crucible for TGA Sample Carrier (HTP40000A64.000-00/-010.00) Crucibles for TGA Sample Carrier (HTP40000A60.000-00) for Hanging Samples of the STA 449 F1/F3 Jupiter® – Cage

Material Temp. Range Consisting of Dimensions Order Number Cage ø 12 mm, height 12 mm, wire ø 0.04 mm, Pt Max. 1650°C Cage, net-shaped NGB813037 mesh width 0.12 mm Cage ø 12 mm, height 12 mm, wire ø 0.06 mm, Pt Max. 1650° C Cage, net-shaped NGB813036 mesh width 0.25 mm

TGA sample carrier with Pt cage

Crucibles for TGA Sample Carrier (HTP40000A58.000-00) of the STA 449 F1 Jupiter® with Turbo Pump – Knudsen Cells Crucibles for DTA Sensor1 of the DSC 404 F1/F3 Pegasus® and for TGA2, TGA-DTA3 Sensor of the STA 449 F1/F3 Jupiter®

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume

Duran glass Max. 600°C Ampoule Length after sealing ≈ 34 mm GB461185 Fused silica Max. 1000°C Ampoule Length after sealing ≈ 34 mm GB461177

Al2O3 (99.7) Max. 1700°C Slip-on plate ø 10 mm GB343550

Al2O3 Max. 1700°C Crucible 0.2 ml GB445172

Al2O3 Max. 1700°C Crucible 0.3 ml NGB810411 for NGB810411, Al O Max. 1700°C Lid GB445175 2 3 GB445172

Al2O3 (99.7) Max. 1700°C Crucible 0.3 ml; inner ø 6 mm sixfold pierced NGB813974

Al2O3 (99.7) Max. 1700°C Crucible 0.9 ml GB445215

Al2O3 (99.7) Max. 1700°C Lid for GB445215 GB445216 Pt/Ir Max. 1600°C Crucible 0.3 ml GB280062 Pt/Ir Max. 1600°C Lid for GB280062 GB280066 > 2200°C Graphite Max. 2400°C Crucible 0.3 ml evaporation GB399222 may occur Only in inert Fine steel Max. 600°C Crucible 0.3 ml GB440112 atmosphere Fine steel Max. 600°C Lid for GB440112 GB440113

1 DTA sample carrier of the DSC 404 F1/F3 Pegasus®: order no. DSC404F1AXX.000-00 (XX = 56, 57 or 68) 2 TGA sample carrier of the STA 449 F1/F3 Jupiter®: order no. HTP40000A58.000-00 3 TGA-DTA sample carrier of the STA 449 F1/F3 Jupiter®: order no. HTP40000AXX.000-00 (XX = 56, 68, 51, 50 or 65)

TGA-DTA crucibles Ampoules for TGA and slip-on plates and TGA-DTA measurements 29 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® TGA-DTA, DSC and TGA-DSC Crucibles

Crucibles for TGA-DTA Sensor (HTP40000A53.000-00) of the STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® (DSC404F1A53.000-00)

Temperature Material Consisting of Dimension/ Volume Remarks Order Number Range Wall thickness 0.3 mm, only Tungsten Max. 2400°C Crucible 80 μl GB453520 for STA 449 F3 Jupiter® Wall thickness 0.2 mm, Tungsten Max. 2400°C Crucible 80 μl NGB808999 BN liner available Tungsten Max. 2400°C Lid Pierced, for NGB808999 NGB809406 BN Max. 2000°C Liner 80 μl For NGB808999 NGB805943 Graphite Max. 2400°C Crucible 0.15 ml GB427607 Graphite Max. 2400°C Lid Pierced, for GB427607 NGB814940

Al2O3 Max. 1700°C Crucible 0.15 ml GB399147

ZrO2 Max. 2000°C Crucible 0.15 ml GB399148

TGA-DTA crucibles for highest temperatures

Crucibles for All DSC and TGA-DSC Sensors of the STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus®

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume

PtRh/Al2O3 Max. 1700°C Crucible + liner + lid For metal melts and other reactive materials 6.225.6-93.2.00 Crucible liner Al O Max. 1700°C 6.225.6-93.1.00 2 3 (spare for 6.225.6-93.2.00) Yttriumoxid- Coating of crucibles for - Content 360g - NGB804075 Spray* increased oxidation stability Crucible liner MgO Max. 1500°C Minimum sale 10 pieces NGB812638 (spare for GB399205) Crucible liner Y O Max. 1700°C Minimum sale 10 pieces NGB812634 2 3 (spare for GB399205) For reshaping of Tool GB397964 Pt crucibles

Al2O3 (99.7) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399972

Al2O3 (99.7) Max. 1700°C Lid For GB399972 GB399973 Duran glass Max. 600°C Ampoule 80 µl Length after sealing ≈19 mm 6.240.1-93.2.00 Fused silica Max. 1000°C Ampoule 80 µl Length after sealing ≈19 mm NGB815223

* Hazardous material, shipment will cause additional costs.

DSC and TGA-DSC crucible variety

30 Crucibles for DSC and TGA-DSC: STA 449 F1/F3 Jupiter® Sensor Types all Sensors Crucibles for All DSC and TGA-DSC DSCSensors 404 ofF1/F3 the PegasusSTA 449 ®F1/F3 all DSC Jupiter Sensors® and DSC 404 (Continuation)F1/F3 Pegasus® (Continuation)

Material Temperature Dimension/ Consisting of Remarks Order Number (Purity/%) Range Volume

Fused silica Max. 1000°C Crucible ø 6.7 mm / 85 μl GB399974 Fused silica Max. 1000°C Lid For GB399974 GB399975 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 85 μl GB399205 Pt/Rh (80/20) Max. 1700°C Crucible ø 6.8 mm / 0.19 ml Height 6 mm NGB801556 For GB399205 Pt/Rh (80/20) Max. 1700°C Lid GB399860 and NGB801556 Al (99.5) Max. 600°C Concavus pan* ø 5 mm / 30/40 μl NGB814672 Al (99.5) Max. 600°C Concavus lid NGB814673 Al (99.5) Max. 600°C Crucible ø 6.7 mm / 85 μl Set of 100 pieces NGB810405 Al (99.5) Max. 600°C Lid For NGB810405 NGB810406 Gold (99.9) Max. 900°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.3.00 Ag Max. 750°C Crucible + lid ø 6.7 mm / 85 μl 6.225.6-93.4.00

ZrO2 Max. 2000°C Crucible 85 μl CaO-stabilized GB397053

ZrO2 Max. 2000°C Lid For GB397053 GB397052 >2200°C evaporation Graphite Max. 2400°C Crucible 85 μl GB399956 may occur Graphite Max. 2400°C Lid For GB399956 GB399957 Glassy carbon Max. 2400°C Crucible ø 6 mm / 50 μl NGB811386 Glassy carbon Max. 2400°C Lid For NGB811386 NGB812613 ø 6.8 mm, thick 0.2 Inhibits sticking of Pt onto Al O Max. 1700°C Washer NGB811071 2 3 mm sensor type S and B Minimum sale MgO Max. 1500°C Crucible ø 6.7 mm, 85 μl NGB812639 10 pieces For NGB812639, MgO Max. 1500°C Lid NGB812637 min. sale 10 pieces

Y2O3 Max. 1700°C Crucible ø 6.7 mm, 85 μl Minimum sale 10 pieces NGB812636 For NGB812636, Y O Max. 1700°C Lid NGB812635 2 3 min. sale 10 pieces BN Max. 2000°C Crucible ø 6.7 mm, 85 μl Inert gas required NGB808836 BN Max. 2000°C Lid For NGB808836 NGB808835 Mo Max. 2000°C Crucible ø 6.8 mm, 85 μl NGB808165

* Using Concavus pans with ASC instrument which were delivered before 2014 may require re-adjustment of the ASC gripper.

31 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® Crucibles for Operation with the Automatic Sample Changer (ASC)

Crucibles for STA 449 F1/F3 & DSC 404 F1/F3 in ASC Operation

ASC Gripper TGA-DSC TGA Sensor2 Crucible Material (Purity/%), Volume STA 449 F1/F3 Sensor* HTP40000A67.000-00 Order Number Lid DSC 404 F1/F3 DSC Sensor** HTP40000A75.000-00 Al (99.5), 30/40 μl (Concavus pan) -3 x x DSC214A66.010.00 Crucible with welded lid -3 x x Al (99.5), 25/40 μl -1 x x 6.239.2-64.5.00 Crucible with welded lid - x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.51.00 Crucible with welded lid x x x Al (99.5), 25/40 μl -1 x x 6.239.2-64.8.00 Crucible and lid with laser-cut-hole - x x Al (99.5), 25/40 μl (500/pkg.) x x x 6.239.2-64.81.00 Crucible and lid with laser-cut-hole x x x Al (99.5), low-pressure, 35 μl -1 x x 6.240.10-65.1.00 Crucible with welded lid - x x CrNi steel (AISI 302), x x x 6.240.1-68.1.00 medium-pressure, 120 μl Crucible with lid x x x Copper, 25 μl - x x 6.239.2-64.6.00 CrNi steel (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.3.00 27 μl, gold-plated, 100 bar CrNi steel (AISI 316L), high-pressure, 27 μl, x x Only for manual operation 6.239.2-93.3.00 100 bar CrNi (AISI 316L), high-pressure, x x Only for manual operation 6.239.2-92.8.00 100 μl, gold-plated, 100 bar CrNi (AISI 316L), high-pressure, 100 μl, x x Only for manual operation 6.239.2-93.4.00 100 bar Ti (Grade 4), high-pressure, 27 μl, 100 bar x x Only for manual operation 6.239.2-92.6.00 Ti (Grade 4), high-pressure, 100 μl, 100 bar x x Only for manual operation 6.239.2-92.9.00

Al2O3 (99.7), ø 6.8 mm, 85 μl x x x GB399972 Crucible with lid (note: lid order no.) x x x GB399973 Fused silica, ø 6.8 mm, 85 μl x x x GB399974 Crucible with lid (note: lid order no.) x x x GB399975 Pt/Rh (80/20), ø 6.8 mm, 85 μl x x x GB399205 Crucible with lid (note: lid order no.) x x x GB399860 Pt/Rh (80/20), ø 6.8 x 6 mm, 190 μl x x x NGB801556 Crucible with lid (note: lid order no.) x x x GB399860

32 ASC Gripper TGA-DSC TGA Sensor2 Crucible Material (Purity/%), Volume STA 449 F1/F3 Sensor* HTP40000A67.000-00 Order Number Lid DSC 404 F1/F3 DSC Sensor** HTP40000A75.000-00

Al (99.5), ø 6.7 mm, 85 μl x x x NGB810405 Crucible with lid (note: lid order no.) x x x NGB810406 Graphite, ø 6.8mm, 85 μl x x x GB399956 Crucible with lid (note: lid order no.) x x x GB399957 Gold (99.9), ø 6.8 mm, 85 μl x x x 6.225.6-93.3.00 Crucible with lid x x x Silver, ø 6.8 mm, 85 μl x x x 6.225.6-93.4.00 Crucible with lid x x x

ZrO2, ø 6.8 mm, 85 μl x x x GB397053 Crucible with lid (note: lid order no.) x x x GB397052

Y2O3, ø 6.8 mm, 85 μl x x x NGB812636 Crucible with lid (note: lid order no.) x x x NGB812635 MgO, ø 6.8mm, 85 μl x x x NGB812639 Crucible with lid (note: lid order no.) x x x NGB812637

Al2O3 (99.7), ø 8 x 8 mm, 300 μl x - x NGB803698 Crucible with lid (note: lid order no.) x - x NGB808209

Pt/Rh/Al2O3 system with lid x x x 6.225.6-93.2.00 Mo, ø 6.8 mm, 85 μl x x - NGB808165 BN, ø 6.7 mm, 85 μl x x only for manual operation NGB808836 Crucible with lid (note: lid order no.) - x - NGB808835

1 Special gripper for Al crucibles on request

2 For the listed crucibles, the TGA-Sensor requires the slip-on plate made of Al2O3, oder no. NGB809010 3 Using Concavus pans with ASC require re-adjustment of ASC gripper. * TGA-DSC Sensor: HTP40000AXX.000-00 (XX = 63, 66, 73 or 74) ** DSC Sensor: DSC404F1AXX.000-00 (XX = 63, 66, 73 or 74)

33 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® Applications – Special Crucibles for Large Samples, Oxygen-Sensitive Alloys

TG /% DTG /(%/min)

-1,42 % -4,28 % -0,93 % -4,13 % -0,90 % -4,20 % 100 2 Sample: A1 Test on a Fire Insulating Material TG /% Sample: A2 DTG /(%/min)

-1,42 % -4,28 % Sample: A3 80 -4,13 % -47,05 % -0,93 % -4,20 % 100 -0,90 % -47,82 % 0 For TGA measurements on inhomo- 57,9 °C -48,16 % 2 53,4 °C 58,8 °C Sample: A1 geneous materials or ones with low Sa765m,0p °lCe: A2 60 764,6 °C Sa765m,2p °Cle: A3 densities (e.g., foams), very large crucibles 80 -47510,05,8 % °C 511,9 °C -2 -47,82 % 515,3 °C 0 are available. The example shows 57,9 °C -48,16 % 53,4 °C 40 58,8 °C three samples of a heavily foaming fire -29,49 % 765,0 °C 60 -30,59 % 764,6 °C -29,65 % 765,2 °C -4 510,8 °C 511,9 °C -2 insulation material. It can clearly be seen 515,3 °C 20 that these three samples exhibit identical 40 -12,52 % -13,23 % TGA behavior. Therefore, no significant 326,5 °C -29,49 % -13,15 % -6 -30,59 % -4 318,5 °C -29,65 % 0 310,7 °C fluctuations in the composition of the lot 20 are to be expected. -12,52 % -13,23 % 200 326,5 °40C 0 600 800 1000-13,15 % -6 Temperature /°C 318,5 °C 0 310,7 °C

200 400 600 800 10Crea0te0d with NETZSCH Proteus software Temperature /°C

A ceramic mass (approx. 130 mg) was tested here in the alumina beaker crucible for TGA measurements (heating rate 10 K/min, synthetic air atmosphere) Created with NETZSCH Proteus software

TG *10 -3 /% Ion Current *10 -11 /A Burn-Up of Organics and Carbon

2,5 100005 Resolution for the smallest of TGA Burn-up of organics & carbon -3 -11 steps can be achieved by increasing the 10000TG 0*10 /% -0,001 % Ion Current *10 /A -0,006 % 2,0 sample mass. In this example, quartz 2,5 1000099995 sand was heated at a rate of 20 K/min Burn-up of organics & carbon -0,002 % 1000099990 -0,001 % in synthetic air. The results demonstrate 1,5 327,9 °C -0,006 % 2,0 amu 18 that extremely small mass-loss steps can 999899995 -0,002 % be resolved by using a sample mass of amu 18 / H2O 999899990 1,0 more than 4000 mg. The evolved gases 1,5 327,9 °C 999799985 amu 18 in this example were detected using our ® amu 44 QMS 403 Aëolos . The second mass-loss 99970 amu 1844 //CO H2O2 0,5 99980 1,0 step amounts to 0.006% and is mainly 999699975 due to the burn-up of organics and amu 44 0 carbon (CO : u 44 and water: u 18). 999699970 amu 44 /CO2 0,5 2 200 400 600 800 1000 1200 Temperature /°C 99965

Quartz sand (4099.46 mg) was tested here in the alumina beaker crucible for TGA measurements 0 99960 200 400 600 800 1000 1200 Temperature /°C Please note: In applications where even larger crucibles are required, we recommend our Multiple-Module Calorimeter, MMC 274 Nexus®. This tabletop instrument bridges the gap between large adiabatic reaction calorimeters and small differential scanning calorimeters. It allows for large sample volumes, while quickly and precisely analyzing properties such as heat capacities. It is also capable of quantitatively characterizing exothermic and endothermic effects.

34 Phase Transformation of an Oxygen-Sensitive Material

The high-performance metal γ-TiAl is resistant to corrosion and high temperatures and has a low specific weight. However, it is highly sensitive to oxygen, so DSC measurements have to be carried out in a very pure atmosphere. Additionally, measurement results can be improved by using the right crucible. Metallic crucibles with high thermal conductivities and low time constants cannot be used for metals. In order to maintain the advantages of a Pt crucible and to prevent reaction between the sample Phase transitions in γ-TiAl. Only a pure oxygen-free atmosphere leads to well-defined phase transitions at and crucible material, a special Pt higher temperatures because oxidation of the metal alloy is inhibited. crucible with an Al2O3 liner is available. The DSC 404 F3 Pegasus®, with its vacuum-tight design and various sensor and crucible types, completely fulfills all measurement requirements for highly oxygen-sensitive materials. In addition, an oxygen trap system (OTS®) is available to further reduce oxygen traces in the atmosphere.

The DSC curve of γ-TiAl shows

The crucible combination of PtRh/Al2O3 an endothermic effect at a peak (order no. 6.225.6-93.2.00) can be temperature of 1323°C. This is due to used for samples which may react with the α2 → α transition. At 1476°C, the Pt up to 1700°C. In addition to the α → β transition occurs and is followed

Al2O3 liner, MgO and Y2O3 liners are by melting of the sample. also available.

Furthermore, these crucible combinations are suitable for cp determination on metals or other oxygen-sensitive materials up to 1400°C.

The reshaping tool for the PtRh crucible (order no. GB397964) can be used to reshape it after measurement, allowing it to be used multiple times.

35 STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus® Applications – Special Crucibles for High Temperatures

Oxidation and Corrosion Studies on Metals

For oxidation and corrosion studies, it is preferable to have a large sample surface in order to maximize the gas access. TGA and TGA-DTA sample holders are available which allow the sample to be attached in a hanging position (TGA: HTP40000A60.000-00; TGA-DTA: HTP40000A61.000-00). The samples can be a plate, mesh, or a compact body which can be encased in a platinum basket.

Steel Corrosion TG /% [1.3] 100,10 This TGA measurement shows several Steel corrosion in oxidative atmosphere

1.9 g, 5 K/min, 16 % O2 in N2, 110 ml/min heating cycles on a hanging steel 100,08 sample. The steel sheet was heated Mass Change: 0,150% 100,06 at a rate of 5 K/min in a nitrogen atmosphere with 16% oxygen. 100,04 Oxidation (mass increase) decreases

Mass Change: 0,082% with each subsequent heating cycle. At 100,02 the beginning of the test, oxidation of the sheet surface occurs. This can be 100,00 1st heating observed in the early onset and rapid 99,98 mass increase for the first heating. 3rd heating Mass Change: 0,066% After a couple of heating cycles, inner 99,96 5th heating oxidation occurs, which is indicated

200 400 600 800 1000 1200 by a slower, diffusion-dependent mass Temperature /°C increase. Hanging the sample in the

Increased sample surface for oxygen access improves oxidation tests special holder maximizes the accessible sample surface and therefore improves oxygen access to all sample sides. This is a prerequisite for certain analyses, such as kinetic studies of the oxidation behavior.

36 Melting Point Determination on Vanadium

In this example, the melting point of a vanadium sample (99.7%) was determined with the STA 449 F1 ® Jupiter . ZrO2 crucibles were used. Melting occurs at an onset temperature of 1886°C. During cooling, the sample recrystallizes with only a small supercooling effect at 1878°C.

Vanadium melting point determination in ZrO2 crucibles

Technical Rhodium Wire – Failure Analysis at High Temperatures

Here, a failure analysis on a rhodium wire was carried out with the STA 449 F1 Jupiter®. The wire material

was measured in ZrO2 crucibles up to 2000°C in a helium atmosphere. The broad double peak and temperatures (1908°C and 1933°C) confirm that the wire material is not made of pure rhodium.

Double melting peak of a technical rhodium wire

37 Sensors and Sample Carriers

38 DSC, TGA-DSC Sensors and TGA Sample Carriers

Nearly all DSC, TGA and STA Choosing the right thermocouple can instruments allow measurements with thus improve the measurement curve exchangeable DSC and DTA or TGA, and also the evaluated test results, so TGA-DTA and TGA-DSC sensors and this should be as carefully considered as sample carriers which cover different the temperature range. temperature ranges. Additionally, the instruments differ in the types of The following pages give an overview thermocouple which are compatible of the DTA, DSC, TGA, TGA-DSC and with them, as well as their ability to TGA-DTA sensors and sample carriers accommodate large crucibles. for these instruments: The type of thermocouple selected influences the sensitivity and resolution DSC 204 F1 Phoenix® of a given DSC or STA system. DSC 404 F1/F3 Pegasus® STA 449 F1/F3 Jupiter® TG 209 F3 Tarsus® TG 209 F1 Libra®

39 DSC 204 F1 Phoenix® Sensors, TG 209 F1 Iris®/Libra® and TG 209 F3 Tarsus® Sample Carriers

DSC 204 F1 Phoenix®

Sensor Type Temperature Range Remarks Order Number

τ-sensor -180°C to 700°C Complete system, ready for installation → High-resolution sensor 6.240.10-09.0.00 μ-sensor -150°C to 400°C Complete system, ready for installation → High-sensitivity sensor 6.240.10-11.0.00

τ-sensor with low μ-sensor with time constant and extremely high very good sensitivity sensitivity for standard applications

TG 209 F1 Iris® – Up to Instrument number 220 10 76

Sample Carrier Material Temperature Sensor Type Remarks Order Number

Al2O3 Type P SiO2-coated, up to instrument No. 220 10 031 6.220.10-57.1.00

Al2O3 Type P SiO2-coated, from instrument No. 220 10 032 on 6.220.10-57.5.00 SiO -coated, for large samples, up to instrument Al O Type P 2 6.220.10-58.1.00 2 3 No. 220 10 031 SiO -coated, for large samples, from instrument Al O Type P 2 6.220.10-58.5.00 2 3 No. 220 10 032 on

Radiation shield Made of Al2O3, complete with metallic flange 6.220.10-04.4.00

Standard sample carrier and radiation shield for corrosive media TG 209 F1 Iris® (from Instrument Number ≥ 220 10 077*) / TG 209 F1 Libra® and TG 209 F3 Tarsus®**

Sample Carrier Material Temperature Sensor Type Remarks Order Number

Higher sensitivity for c-DTA®, with SiO coating, Al O Type P 2 6.220.10-60.0.00** 2 3 including radiation shield Higher sensitivity for c-DTA®, with SiO coating, Al O Type P 2 6.220.10-60.1.00 2 3 without radiation shield Higher sensitivity for c-DTA®, for large samples, Al O Type P 6.220.10-61.0.00** 2 3 including radiation shield Higher sensitivity for c-DTA®, with SiO coating, Al O Type P 2 6.220.10-61.1.00 2 3 without radiation shield

Radiation shield Made of Al2O3, from instrument No. 77 to 158 6.220.10-60.2.00

Radiation shield Made of Al2O3, from instrument No. 159 on 6.220.10-60.3.00

Al2O3 Type P Sample support made of Al2O3, including radiation shield 6.220.10-62.0.00**

Al2O3 Type P Sample support made of Al2O3, without radiation shield 6.220.10-62.1.00 For large samples, sample supports made of Al O , Al O Type P 2 3 6.220.10-63.0.00 2 3 radiation shield For large samples, sample supports made of Al O , Al O Type P 2 3 6.220.10-63.1.00 2 3 without radiation shield For crucible up to an outer diameter of 9 mm, with protected thermocouple, particulary suitable for corrosive Al O Type P 6.220.10-66.0.00 2 3 media, including radiation shield and crucible made of

Al2O3 with ø 8 mm (0.3 ml, order no. NGB803698) For crucible up to an outer diameter of 9 mm,

Al2O3 Type P with protected thermocouple, particulary suitable 6.220.10-66.1.00 for corrosive media Standard sample carrier with closed stuck head plate,

Al2O3 Type P particularly suitable for corrosive media, 6.220.10-65.0.00** including radiation shield

Made of Al2O3, Radiation shield from instrument: TG 209 F1 Iris® no. 77 up to 158, 6.220.10-60.2.00** TG 209 F3 Tarsus® no. 010 up to 048 ® Made of Al2O3, for TG 209 F1 Libra , Radiation shield from instrument TG 209 F1 Iris® no. 77 up to 159; 6.220.10-60.3.00** for TG 209 F3 Tarsus® no. 049 * Please contact us for sample carriers for instrument number 1 to 76. ** also for TG 209 F3 Tarsus®

Sample carrier type P and radiation shield

41 c‐DTA® – More Than an Easy Calibration Routine

c-DTA® – Temperature Calibration and Determination of Caloric Effects in TGA Measurements

The calculated DTA/DSC-signal, c-DTA®, Thus, correlation of such results is not is ideal for easy temperature calibration influenced by the hardware. without the need for magnetic Curie point standards, which would often All TGA sample carriers (TG 209 F1 necessitate partial disassembling of the Iris®/Libra®, TG 209 F3 Tarsus®, STA thermobalance. In addition, signals of 449 F1/F3 Jupiter®) allow for c-DTA® mass change together with endo- and determination. exothermal behaviors (e.g., vaporization Ceramic and metallic crucibles are with mass loss or melting without mass available to achieve optimum peak change) can be obtained without any temperature results together with the hardware add-ons. caloric information on the tested sample.

42 Thermal Behavior of a Large Steel Sample

In this example, a large steel sample (1018.59 mg) was tested with the STA 449 F1 Jupiter® at a heating rate of 20 K/min in an argon atmosphere. A slip-on plate made of alumina (ø 17 mm) was used to carry the sample.

The c-DTA® curve (blue) shows an endothermic effect at 1362°C which corresponds to melting of the sample. In the same temperature range, the TGA curve (green) indicates some minor mass loss (0.02%) which is due to a small Measurements of large sample masses can be done with slip-on plates. Various dimensions of such evaporation effect. plates are available.

Melting and Decomposition of HDPE with the TG 209 F1 Libra®

High density polyethylene (HDPE) was here measured with the TG 209 F1 Libra® at a heating rate of 10 K/min in

an N2 atmosphere. The sample mass amounted to 10.31 mg. Before decomposition started at approx. 420°C (green), the c-DTA® curve (red) detected the melting peak at 128.8°C. Under the same conditions, the melting peak temperature of HDPE was determined with the DSC 200 F3 Maia® (black curve). As can be observed, the two sets of results are in perfect agreement.

Very good correlation between calculated and measured melting peak temperature

43 DSC 404 F1/F3 Pegasus® DTA and DSC Sensors

DTA Sensors for the DSC 404 F1/F3 Pegasus®

Sensor Type Temperature Range Crucible/Volume/Order Number Radiation Shield Order Number

Type S 25°C to 1650°C 2x Al2O3, 0.2 ml, GB445172 Integrated DSC404F1A56.000-00 Type S, protected 25°C to 1500°C 2x Al O , 0.2 ml, GB445172 Integrated DSC404F1A68.000-00 thermocouples 2 3

Type B 25°C to 1750°C 2x Al2O3, 0.2 ml, GB445172 Integrated DSC404F1A57.000-00 W3%Re/W25%Re 25°C to 2000°C 2x tungsten, GB453520 Integrated DSC404F1A53.000-00 (exchangeable)

® DSC Sensors for the DSC 404 F1/F3 Pegasus – for Standard & cp Measurements*

Sensor Type Temperature Range Crucible/Volume/Order Number Radiation Shield Order Number

2x PtRh crucible, GB399205, Type S, lid GB399860 25°C to 1650°C Integrated DSC404F1A54.000-00 round design 2x Al2O3 crucible, GB399972, lid GB399973 2x Al O crucible, GB399972, Type P -150°C to 1000°C 2 3 Integrated DSC404F1A59.000-00 lid GB399973 -150°C to 700°C, inert 2x Al O crucible, GB399972, Type E 2 3 Integrated DSC404F1A70.000-00 -150°C to 500°C, oxidizing lid GB399973 -150°C to 800°C, inert 2x Al O crucible, GB399972, Type K 2 3 Integrated DSC404F1A71.000-00 -150°C to 500°C, oxidizing lid GB399973 2x PtRh crucible, GB399205, lid GB399860 Type S 25°C to 1650°C Integrated DSC404F1A72.000-00 2x Al2O3 crucible, GB399972, lid GB399973 2x PtRh crucible, GB399205, lid GB399860 Type B 25°C to 1750°C Integrated DSC404F1A76.000-00 2x Al2O3 crucible, GB399972, lid GB399973 Type K, -150°C to 800°C, inert 2x Al O crucible, GB399972, 2 3 Integrated DSC404F1A77.000-00 octagonal -150°C to 500°C, oxidizing lid GB399973 2x PtRh crucible, GB399205, Type S, lid GB399860 25°C to 1650°C Integrated DSC404F1A78.000-00 octagonal 2x Al2O3 crucible, GB399972, lid GB399973 Type E, -150°C to 700°C, inert 2x Al O crucible, GB399972, 2 3 Integrated DSC404F1A79.000-00 octagonal -150°C to 500°C, oxidizing lid GB399973

* cp recommended up to 1400°C

44 DSC Sensors for the DSC 404 F1/F3 Pegasus® – for ASC Operation, Octagonal Design

Sensor Type cp Temperature Range Crucible/Volume/Order Number Radiation Shield Order Number 2x PtRh crucible, GB399205, Type S, lid GB399860 Yes 25°C to 1650°C Integrated DSC404F1A73.000-00 round design 2x Al2O3 crucible, GB399972, lid GB399973 2x PtRh crucible, GB399205, lid GB399860 Type P Yes -150°C to 1000°C Integrated DSC404F1A75.000-00 2x Al2O3 crucible, GB399972, lid GB399973 150°C to 800°C, inert 2x Al O crucible, GB399972, Type K Yes -150°C to 500°C, 2 3 Integrated DSC404F1A74.000-00 lid GB399973 oxidizing

DTA sensor DSC sensor in round DSC sensor DSC sensor in with protected design with Pt crucibles octagonal design thermocouples for ASC operation

45 STA 449 F1/F3 Jupiter® TGA Sample Carriers and TGA-DTA Sensors

TGA Sample Carriers for the STA 449 F1/F3 Jupiter® – for Standard Measurements

Temperature Radiation Material/Sensor Type Crucible/Volume/Order Number Order Number Range Shield

Type P -150°C to 1000°C Al2O3, 3.4 ml, GB445213 Included HTP40000A55.000-00 Type P -150°C to 1000°C - Without HTP40000A55.010-00

Type S 25°C to 1650°C Al2O3, 3.4 ml, GB445213 Included HTP40000A58.000-00 Type S 25°C to 1650°C - Without HTP40000A58.010-00

Made of Al2O3, W3%Re/W25%Re 25°C to 1650°C Al2O3, 3.4 ml, GB445213 Included HTP40000A62.000-00

Made of Al2O3, W3%Re/W25%Re 25°C to 1650°C - Without HTP40000A62.010-00 Crucible required: Made of fused silica, type S 25°C to 1100°C Included HTP40000A64.000-00 Fused silica, 3.4 ml, NGB811507 Made of fused silica, type S 25°C to 1100°C - Without HTP40000A64.010-00 W3%Re/W25%Re 25°C to 2400°C Tungsten, NGB809001 Included HTP40000A52.000-00 W3%Re/W25%Re 25°C to 2400°C - Without HTP40000A52.010-00 Radiation shield from tungsten 25°C to 2400°C - Complete HTP40000A53.020-00

TGA type S sample carrier with different crucibles and plates, TGA type W sample carrier (W3%Re/W25%Re); for more crucibles and plates, see TGA crucibles table.

46 TGA Sample Carriers and TGA-DTA Sensors for the STA 449 F1/F3 Jupiter® – with Special Design

Temperature Material/Sensor Type Crucible Type Radiation Shield Order Number Range TGA, type S, length 250 mm, for 25°C to 1650°C Al O slip-on plate, ø 17 mm Included HTP40000A57.000-00 water vapor furnace HTP40000A88 2 3 TGA, type S, length 250 mm, for 25°C to 1000°C - Without HTP40000A57.010-00 water vapor furnace HTP40000A88 TGA, made of Al O , type S, 2 3 Options: net-shaped for hanging samples, 25°C to 1650°C Included HTP40000A60.000-00 cage made of Pt, sample size max. 13 x 20 mm order no. NGB813036 or TGA, made of Al O , type S, 2 3 order no. NGB813037 for hanging samples, 25°C to 1650°C Without HTP40000A60.010-00 (see page 29) sample size max. 13 x 20 mm TGA, made of Al O , type S, for Special container made of 2 3 tube made of glass measurements in an immersion bath Al O , 3 immersion container 25°C to 1650°C 2 3 (single order no. HTP40000B60.000-00 (e.g., salt solution), for hanging made of Pt and 5 immersion NGB801706) samples container made of BN TGA-DTA, type S, hanging samples 25°C to 1650°C Included HTP40000A61.000-00 TGA-DTA, type S, hanging samples 25°C to 1650°C Without HTP40000A61.010-00

TGA-DTA sensor TGA sample carrier TGA sample carrier for for hanging samples for hanging samples measurements in an immersion bath

47 STA 449 F1/F3 Jupiter® TGA-DTA and TGA-DSC Sensors

TGA-DTA Sensors for the STA 449 F1/F3 Jupiter® – for Standard Measurements

Temperature Range/ Sensor Type Crucible/Volume/Order Number Radiation Shield Order Number Atmosphere -150°C to 700°C, inert Type E 2x Al O , 0.2 ml, GB445172 Included HTP40000A50.000-00 -150°C to 500°C, oxidizing 2 3 -150°C to 700°C, inert Type E - Without HTP40000A50.010-00 -150°C to 500°C, oxidizing -150°C to 700°C, inert Type K 2x Al O , 0.2 ml, GB445172 Included HTP40000A51.000-00 -150°C to 500°C, oxidizing 2 3 -150°C to 700°C, inert Type K - Without HTP40000A51.010-00 -150°C to 500°C, oxidizing

Type S 25°C to 1650°C 2x Al2O3, 0.2 ml, GB445172 Included HTP40000A56.000-00 Type S 25°C to 1650°C - Without HTP40000A56.010-00 Type S, protected 25°C to 1500°C 2x Al O , 0.2 ml, GB445172 Included HTP40000A68.000-00 thermocouples 2 3 Type S, protected 25°C to 1500°C - Without HTP40000A68.010-00 thermocouples 25°C to 1650°C, W3%Re/W25%Re 2x Al O , 0.2 ml, GB445172 Included HTP40000A65.000-0 not for oxidizing atmospheres! 2 3 25°C to 1650°C, W3%Re/W25%Re - Without HTP40000A65.010-0 not for oxidizing atmospheres! 2x tungsten, NGB808999, wall thickness 0.2 mm; 25°C to 2000°C, W3%Re/W25%Re ® Included HTP40000A53.000-00 not for oxidizing atmospheres! optional for STA 449 F3 Jupiter : tungsten crucible, with wall thickness 0.3 mm, GB453520 25°C to 2000°C, W3%Re/W25%Re - Without HTP40000A53.010-00 not for oxidizing atmospheres!

TGA-DTA sensors with different crucibles and plates, TGA-DTA sensor Type W (W3%Re/ W25%Re); for more crucibles, please see TGA

48 TGA-DSC Sensors for the STA 449 F1/F3 Jupiter® – for Standard Measurements

Temperature Range/ Sensor Type Crucible/Volume/Order Number Radiation Shield Order Number Atmosphere 2x Al O , 85 μl, Type P -150°C to 1000°C 2 3 Included HTP40000A59.000-00 crucible GB399972, lid GB399973 Type P -150°C to 1000°C - Without HTP40000A59.010-00 2x Al O , 85 μl, Type S 25°C to 1650°C 2 3 Included HTP40000A69.000-00 crucible GB399972, lid GB399973 Type S 25°C to 1650°C - Without HTP40000A69.010-00 -150°C to 700°C, inert 2x Al O , 85 μl, Type E 2 3 Included HTP40000A70.000-00 -150°C to 500°C, oxidizing crucible GB399972, lid GB399973 -150°C to 700°C, inert Type E - Without HTP40000A70.010-00 -150°C to 500°C, oxidizing Type E -150°C to 700°C, inert 2x Al O , 85 μl, 2 3 Included HTP40000A79.000-00 octagonal -150°C to 500°C, oxidizing crucible GB399972, lid GB399973 Type E -150°C to 700°C, inert - Without HTP40000A79.010-00 octagonal -150°C to 500°C, oxidizing -150°C to 700°C, inert 2x Al O , 85 μl, Type K 2 3 Included HTP40000A71.000-00 -150°C to 500°C, oxidizing crucible GB399972, lid GB399973 -150°C to 700°C, inert Type K - Without HTP40000A71.010-00 -150°C to 500°C, oxidizing Type K -150°C to 800°C, inert 2x Al O , 85 μl, 2 3 Included HTP40000A77.000-00 octagonal -150°C to 500°C, oxidizing crucible GB399972, lid GB399973 Type K -150°C to 800°C, inert - Without HTP40000A77.010-00 octagonal -150°C to 500°C, oxidizing

Different TGA-DSC Sensors

49 Radiation Shield for STA Systems

Radiation Shield with 3 Supporting Bars

Component parts Order number 1 Radiation shield – Complete HTP40000A72.040-00

1 Supporting bar made of Al2O3 GB348216 2 2 Disk for radiation shield

made of Al2O3 NGB809780

3 Disk for radiation shield made of nickel NGB809779

4 Spacing tube made of Al2O3 GB351383 3

5 Metal base for radiation shield HTP40000A72.040-03

50 Radiation Shield with 2 Supporting Bars

1 Component parts Order number

1 Supporting bar made of Al O GB348216 2 2 3 2 Disk for radiation shield NGB806979

made of Al2O3

3 3 Disk for radiation shield NGB806987 made of nickel

4 Distance tube made of Al2O3 GB351383 4 5 Metal base for radiation shield HTP40000A72.020-01

51 STA 449 F1/F3 Jupiter®

TGA and TGA-DSC Sensors for cp Determination and Operation with the Automatic Sample Changer (ASC)

® TGA-DSC Sensors for the STA 449 F1/F3 Jupiter – for cp Determination (Recommended up to 1400°C)

Temperature Range/ Radiation Sensor Type Crucible/Volume/Single Order Number Order Number Atmosphere Shield Type S, round design, 2x PtRh crucible, GB399205, lid GB399860 25°C to 1650°C Included HTP40000A54.000-00 especially for cp 2x Al2O3 crucible, GB399972, lid GB399973 Type S, round design, 25°C to 1650°C - Without HTP40000A54.010-00 especially for cp 2x PtRh crucible, GB399205, lid GB399860 Type S 25°C to 1650°C Included HTP40000A72.000-00 2x Al2O3 crucible, GB399972, lid GB399973 Type S 25°C to 1650°C - Without HTP40000A72.010-00 Type S 2x PtRh crucible, GB399205, lid GB399860 25°C to 1650°C Included HTP40000A78.000-00 octagonal version 2x Al2O3 crucible, GB399972, lid GB399973 Type S 2x PtRh crucible, GB399205, lid GB399860 25°C to 1650°C Without HTP40000A78.010-00 octagonal version 2x Al2O3 crucible, GB399972, lid GB399973 2x PtRh crucible, GB399205, lid GB399860 Type B 25°C to 1750°C Included HTP40000A76.000-00 2x Al2O3 crucible, GB399972, lid GB399973 Type B 25°C to 1750°C - Without HTP40000A76.010-00

TGA-DSC sensors for cp determination

52 STA 449 F1/F3 Jupiter®

TGA and TGA-DSC Sensors for cp Determination and Operation with the Automatic Sample Changer (ASC)

TGA, TGA-DTA and TGA-DSC Sensors for the STA 449 F1/F3 Jupiter® – for Operation with the Automatic Sample Changer (ASC) Temperature Range/ Radiation Sensor Type Crucible/Volume/Single Order Number Order Number Atmosphere Shield 2x PtRh crucible, GB399205,lid GB399860 TGA-DSC, Type P -150°C to 1000°C Included HTP40000A63.000-00 2x Al2O3 crucible, GB399972,lid GB399973 TGA-DSC, Type P -150°C to 1000°C - Without HTP40000A63.010-00 -150°C to 700°C, inert 2x Al O , 85 μl, TGA-DSC, Type E 2 3 Included HTP40000A66.000-00 150°C to 500°C, oxidizing crucible GB399972, lid GB399973 -150°C to 700°C, inert TGA-DSC, Type E - Without HTP40000A66.010-00 -150°C to 500°C, oxidizing TGA-DSC, Type S, 2x PtRh crucible, GB399205, lid GB399860 25°C to 1650°C Included HTP40000A73.000-00 for cp 2x Al2O3 crucible, GB399972, lid GB399973 TGA-DSC, Type S, 25°C to 1650°C - Without HTP40000A73.010-00 for cp -150°C to 700°C, inert 2x Al O , 85 μl TGA-DSC, Type K 2 3 Included HTP40000A74.000-00 -150°C to 500°C, oxidizing crucible GB399972,lid GB399973 -150°C to 800°C, inert TGA-DSC, Type K - Without HTP40000A74.010-00 -150°C to 500°C, oxidizing

Spare part: slip-on plate made of Al2O3, NGB809010 TGA, type S 25°C to 1650°C Included HTP40000A75.000-00 Crucible: Al2O3, 85 μl, GB399972 Lid: GB399973 TGA, type S 25°C to 1650°C - Without HTP40000A75.010-00 TGA-DTA, type S, with protected 25°C to 1500°C 2x Al2O3 crucible, GB399972, lid GB399973 Included HTP40000B68.000-00 thermocouples and slip-on plates

Spare part: slip-on plate made of Al2O3, TGA, type P -150°C to 1000°C NGB809010 Included HTP40000A67.000-00

Crucible: Al2O3, 85 μl, GB399972 TGA, type P -150°C to 1000°C - Without HTP40000A67.010-00

TGA-DSC sensor for ASC TGA-DTA sample carrier (with operation protected thermocouples) and slip-on plates for ASC operation

Different Sensor Types Different– The Right Sensor Sensor Types for- For Each Each Application Application the Right Sensor

The STA 449 F1/F3 Jupiter® and DSC ofDifferent only a few Sensor seconds. Types Selection - For Each of the Ofpossibility course, the to easilyvacuum-tight insert different design of can be covered with one and the same 404 F1/F3 Pegasus® systems are rightApplication crucible, togetherthe Right with Sensor the most thesesensor instruments types and sample further carriers extends within the instrument. Of course, the vacuum-tight unique in their flexibility. One of their appropriate furnace out of nine options, measurementonly a few seconds. capabilities Together in the with the design of these instruments further ex- The STA 449 F1/F3 Jupiter and DSC selection of the right furnace out of nine tend the measurement capabilities in the outstanding features is their capability allows a single instrument to cover an temperature range between -150°C 404 F1/F3 Pegasus systems are unique different furnaces and the right crucible temperature range between - for easy insertion of different sensor extremely broad application range. and 2400°C. in their flexibility. One of the out- an extremely wide application range 150°C and 2400150°C. types and sample carriers in a matter standing features is the

Advantages of True DSC Advantages of True DSC Measurements DSC /(µV/mg) Measurements 2.0 ↓ exo True DSC measurements require special True DSC measurements require special Sample: Gold sensors with optimized design end ther- sensors with optimized design and 1.5 thermocouple positioning. They are not mocouple positioning. They are not the same as a calibrated DTA test. sample carrier comparable to a calibrated DTA test. DSC Type S DSC sensors offer a more stable 1.0 DSC sensors offer a more stable base- baseline, a higher sensitivity, an line, a higher sensitivity, an improved improved detection limit, and a detection limit, and a short time con- 0.5 shorter time constant. stant. Therefore, transition peaks are sharp, Therefore, transition peaks are sharp, reliable and easy to separate from 0.0 reliable and easy to separate from the the baseline curvature. sample carrier baseline curvature. DTA Type S DSC sensors can detect weak  DSC sensors can detect weak transi- transitions and glass transition steps -0.5 1030 1040 1050 1060 1070 1080 1090 1100 1110 tions and glass transition steps and and offer excellent reproducibility. Temperature /°C offer excellent reproducibility. DSC and DTA type S sensor comparison DSC-cp sensors are capable of DSC and DTA sensor type S comparison  DSC-cp sensors are capable of meas- measuring the specific heat (cp). uring the specific heat (cp).

Detection of Weak Effects with the Detection of Weak Effects with the High-Temperature DSC Sensor DSC /(mW/mg) High-Temperature DSC Sensor ↓ exo 7 This example shows a DSC DSC measurement of an iron disk be- 6 measurement of an iron disk between Sample: Iron tween room temperature and 1650°C. 1559.7 °C The iron disk was placed in a closed room temperature and 1650°C. The 5 Pt+Al O line closed with a Pt lid. The iron disk was placed in a Pt+Al O liner 2 3 2 3 4 sample mass amounted to 129.68 mg closed with a Pt lid. The sample mass 3 and was heated up in argon atmosphere amounted to 129.68 mg and was 288.1 J/g at a heating rate of 20 K/min. The DSC heated in an argon atmosphere at a 2 1399.3 °C sensor type S is especially designed for rate of 20 K/min. The DSC type S sensor 928.4 °C 1 cp determination and outstands in sensi- is especially designed for c determination 772.0 °C 18 J/g 18.13 J/g p tivity. Even weakest effects such as the and exhibits outstanding sensitivity. 0 1534,0 °C iron solid-solid transitions could be Even the weakest of effects such as -1 clearly detected. iron solid-solid transitions can clearly 200 400 600 800 1000 1200 1400 1600 Temperature /°C be detected. Melting occurs at 1534 °C (onset). DSC measurement of an iron disk up to 1650°C

DSC measurement of an iron disk up to 1650°C

32 DSC /(µV/mg) [2] ↓ exo

Sample: Indium 6 DSC Sensor Types E and S DSC /(µV/mg) 4[2] ↓ exo DSC sensor types E, K and P allow sample carrier 8 DSC Type E sensitivity of DSC Type E measurements with extremely high 2 approximately 15 times higher! sensitivity. sample carrier Sample: Indium DSC Type S 306.8 µVs/mg 6 DSC type S and B sensors have the 0 20.77 µVs/mg advantage of a wide temperature range and a short time constant. 4 140 150 160 170 180 190 200 Temperature /°C sample carrier DSC Type E sensitivity of DSC Type E The DSC signal in the lower temperature 2 approximately 15 times higher! range is approx. 15 times higher for sample carrier sensor type E than for type S. On the DSC Type S 306.8 µVs/mg other hand, the resolution of type S is 0 20.77 µVs/mg very high.

140 150 160 170 180 190 200 Temperature /°C DSC sensor types E and S comparison

DSC Sensor Types P and S DSC /(µV/mg) [1]↓ exo 7 In the lower temperature range up to 1000°C, the DSC sensor type P has Sample: Indium 6 excellent sensitivity and well-pronounced resolution compared to the high- 5 temperature sensor type S. The latter is designed for measurements up to DSC4 /(µV/mg) Sample Carrier [1]↓ exo DSC Type P 1650°C. Its sensitivity increases with DSC sensor types E and S comparison 37 temperature.

Sample: Indium 26 Sensitivity of Type P This example shows that the DSC sensor Sample Carrier approximately 6 times higher! DSC Type S type P is a good alternative to the DSC 15 sensors type E and K (max. 700°C/800°C 174.8 µVs/mg 27.36 µVs/mg 0 in an inert atmosphere) when 4 Sample Carrier DSC Type P temperatures up to 1000°C are required. 140 150 160 170 180 190 3 Temperature /°C Comparison of DSC sensor types P and S 2 Sensitivity of Type P Sample Carrier approximately 6 times higher! DSC Type S 1

174.8 µVs/mg 27.36 µVs/mg 0

140 150 160 170 180 190 Temperature /°C

55 Tungsten for Highest Temperature Applications

Basic Requirements for Highest Temperature Applications

For applications at very high temperatures, No insulation of thermocouples in the Low-Mass Sample Holder Made of critical hardware issues have to be hot zone Tungsten resolved. Ceramic insulation materials Possibility of repairing thermocouples become electrically conductive, on site The low-mass tungsten sample holder thermocouple wires become very brittle, Free access to the sample holder has well-defined heat flow paths and a and for most materials, a potentially for loading sample and reference split geometry for high calorimetric high level of vapor pressure needs to be crucibles sensitivity. The conical sample crucible taken into consideration. Additionally, Good vertical upward purge gas flow fits safely into the massive sample holder metallic parts are sensitive to oxygen to take away all vaporized sample plate. The thermocouple connection and the heat transfer is dominated by products is designed such that no welding is conduction and radiation. These problems Vacuum-tight instrument construction necessary. It is thus possible to measure have certain consequences for the design Contact between crucible and sample the temperature and DTA signal directly of the high-temperature instruments, carrier independent of the atmosphere, and with high accuracy. Additionally, this their sample holders and crucibles radiation and temperature condition sample holder allows for a “crucible-in- by making it necessary to ensure the Possibility of covering samples for crucible” arrangement in order to handle following: unchanged radiation behavior critical samples.

Tungsten – The Material of Vapor pressure Graphite(C), Tungsten (W)

Choice for Highest-Temperature Graphite Tungsten Measurements 1, E-00 At 2400°C, the vapor pressure of 1, E-01 graphite is 10-3 Torr, therefore no high 1, E-02 vacuum can be applied. The tungsten 1, E-03 ® furnace of the STA 449 F1 Jupiter 1, E-04 allows measurements in high vacuum 1, E-05 -5 (10 Torr) up to 2400°C. This is essential log (p/torr) 1, E-06 for clean atmospheres and Knudsen cell tests. 1, E-07 1, E-08 1, E-09 1500 1700 1900 2100 2300 2500 2700 2900 Temperature/°C

56 PureT GSapphire /% at the Highest Temperatures: Tungsten Furnace, Sensor,DTA /(µ andV/m gTungsten) Crucibles

TGA ↓ exo 6 This TGA-DTA measurement on pure 1T00G /% DTA /(µV/mg) sapphire was performed in the tungsten pure Sapphire 5 TGA ↓ exo 6 furnace up to 2100°C. The crucibles 12.34 mg, 75 K/min, He flow, 10800 tungsten crucible with lid 4 were closed with lids, both made of pure Sapphire 5 tungsten. Melting of the pure material 12.34 mg, 75 K/min, He flow, occurred at 2054°C (extrapolated Heat of fusion (lit.) = 1069 J/g 3 8600 tungsten crucible with lid 4 --> calorimetric sensitivity 0.049 µV/mW onset). Determination of the calorimetric 2 sensitivity of the TGA-DTA sensor Type 3 6400 Heat of fusion (lit.) = 1069 J/g Area: 52.62 µVs/mg W was based on this measurement in a --> calorimetric sensitivity 0.049 µV/mW Onset: 2054.2 °C 1 2 helium atmosphere. The calorimetric sensitivity was determined to be 4200 Area: 52.62 µVs/mg DTA 0 Onset: 2054.2 °C 1 0.049 μV/mW. As expected for the pure material, the 200 -1 1900DTA 1950 2000 2050 2100 2150 TGA curve (green) shows no mass loss Temperature /°C before and during melting. 0 -1 1900 1950 2000 2050 2100 2150 Temperature /°C

Melting of a pure sapphire sample

Alumina Fibers at the Highest Temperatures: Tungsten Sensor and Tungsten Crucibles

Tungsten has a lower vapor pressure TG /% DTA /(µV/mg) [2.2] compared to graphite and is therefore ↓ exo the material of choice when very 110 Sample: Alumina Fibers TG /% DTA /(µV/mg) high-end temperatures are required. Sample Carrier: Type W [2.20] 2047.3 °C ↓ exo This TGA-DTA measurement was 105 DTA heating 110 Sample: Alumina Fibers performed with the tungsten furnace Sample Carrier: Type W 0-5 and sensor type W3%Re/W25%Re. DTA cooling 2047.3 °C 100 105 DTA heating Alumina fibers (6.8 mg) in the tungsten crucible were heated to 2100°C and --510 95 DTA cooling 100 -1.10 % then cooled in a helium atmosphere. Upon heating, an endothermic effect 90 --105 95 occurred at 2047°C (peak temperature) -1.10 % which can be attributed to melting of 85 90 --1250 the alumina fiber sample. Upon cooling, recrystallization occurred at 1936°C 1935.6 °C 80 85 (peak temperature). A slight mass loss 1900 1950 2000 2050 -20 Temperature /°C was detected above 1900°C which was 1935.6 °C Melting80 and recrystallization of alumina fibers observed in the DTA signal. Small mass loss indicates probably due to partial evaporation of evaporation of the sample.1900 1950 2000 2050 the sample. Temperature /°C

57 STA 449 F1/F3 Jupiter® and DSC F1/F3 Pegasus® Special Sample Carriers for Special Applications – OTS®

Oxygen Trap System – OTS®

® The OTS oxygen trap system, for the ring is capable of almost entirely elimi- Residual O2 level is a function of: STA 449 F1/F3 Jupiter® and DSC 404 nating the residual oxygen after F1/F3 Pegasus® systems removes traces evacuation. Vacuum tightness of the instrument

of residual oxygen in the gas Desorption of O2 from the walls atmosphere inside the instrument. Such low oxygen concentrations cannot Vacuum tightness of the gas supply A residual oxygen content of <1ppm be achieved unless the instrument is Purity of the purge gas can be achieved. vacuum-tight and equipped with an evacuation system. Both of these A ceramic substrate bearing a getter requirements are fulfilled by the STA ring is mounted on the sample carrier or 449 F1/F3 Jupiter® and DSC 404 F1/F3 in the sample carrier tube. This getter Pegasus® systems.

TGA-DSC Sensor

Getter material -ring-

Getter support

Radiation shield

58 OTS® – for STA 449 F1/F3 Jupiter® and DSC 404 F1/F3 Pegasus®

Instrument Order Number

STA – OTS® getter support and ring HTP40000A97.010-00 DSC – OTS® getter support and ring HTP40000A98.010 STA/DSC – getter ring (for ordering separately) NGB809270

Please note: The OTS® system can be used with all sensor types. Restrictions may occur with sensor type P when used with the steel and silver furnace. Please contact your sales & service representative for details.

Oxidation of Zirconium TG /mg Temp. /°C [1.2] In this example, a zirconium sample 1200 0.8 (190.0 mg) was measured with the STA 449 F1 Jupiter® in a helium atmosphere 1000 0.6 under isothermal conditions (1000°C). With OTS-System 800 Without OTS-System oxidation without OTS 0.4 After three hours, oxidation of the Zr

600 sample (red curve) led to a total mass 0.2 increase of approx. 0.38 mg when no -0.008 mg ® 400 OTS was used. 0.0 with OTS, no significant oxidation any more

200 When the OTS® system was applied to -0.2 the sample carrier for a measurement 0 on the same sample mass, however, no 60 80 100 120 140 160 Time /min significant oxidation occurred (green curve). The mass increase was determined STA measurement of zirconium under isothermal conditions to amount to only 0.008 mg.

59 STA 449 F1/F3 Jupiter® and DSC F1/F3 Pegasus® Special Sample Carriers for Special Applications – Hanging Samples

Large Sample Surface – Excellent Advantages of the Sample Carrier Atmospheric Access for Hanging Samples

The special TGA sample carrier and TGA- Sample can be hung down directly DTA sensor for hanging or suspended Bendable thermocouple type S samples allow perfect access to all sample Improved contact between the surfaces by the atmosphere. sample and purge gas Sample dimensions up to

These Al2O3 sample carriers and sensors 13 x 20 mm

with Al2O3 frame are available for the Very slow mass increase detectable STA 449 F1/F3 Jupiter® systems (μg/hour range) (TGA order no. HTP40000A60.000-00; Long-term signal stability, typical drift TGA-DTA order no. HTP40000A61.000-00). less than 0.1μg/h Choice of atmosphere:

The sample carrier is easy to handle and O2 allows selection of the hanging wires Corrosive according to the sample properties. Controlled humidity

TGA-DTA sensor TGA sample for hanging carrier with samples Pt cage

60 37

Large Sample Surface -Excellent At- Advantages of the sample carrier for mosphere Access suspended samples

Perfect access of atmosphere to the en-  Sample can be directly hanged down tire sample surfaces can be achieved  Bendable thermocouple type S with the special TGA sample carrier for  Improved contact between sample and hanging or suspended samples. purge gas

This Al2O3 sample carrier with Al2O3  Sample dimensions up to 13 x frame is available for the STA 449 F1/ 20 mm F3 Jupiter systems (order no.  Very slow mass increase detectable HTP40000A60.000-00 including radia- (µg/hour range) tion shield; HTP40000A60.010-00 with-  Long term signal stability, typical out radiation shield). drift below 0.1 µg/h  Choice of atmosphere: The sample carrier is easy to handle and allows to select the hanging wires ac-  O2 cording to sample properties.  Corrosive with Silica tubes  Controlled humidity with Wet- sys system

TGA Measurement of a Hanging

Coated Glass Sample TG /% DTG *10-3 /(%/min)

In this example, two sheets of a coated 100.1 8 glass sample were pierced and fixed TG 100.0 -0.087 % 6 into the special TGA sample holder for -0.036 % suspended samples. The total sample 99.9 4 mass amounted to 274.99 mg. The two DTG TGA Measurement of a Hanging 99.8 2 sheets were heated up to 600°C in Residual Mass (600.0°C): 99,877% Coated Glass Sample 0 synthetic air (heating rate 5 K/min). 99.7 361.7 °C -2 Two sheets of a coated glass samples 99.6 were pierced and fixed into the special The improved contact between the 398.3 °C -4 TGA sample holder for suspended sam- sample surface and purge gas resulted 99.5 ples. The total sample mass amounted to -6 in the detection of very weak mass-loss 316.0 °C 274.99 mg. The two sheets were heated 99.4 steps at 316°C (0.087%) and 398°C -8 up to 600°C in synthetic air (heating rate

(0.036%). 100 200 300 400 500 600 5K/min). Temperature /°C The improved contact between sample Mass-loss behavior of coated glass sheets surface and purge gas resulted in the detection of very weak mass-loss steps at 316°C (0.087%) and 398°C (0.036%).

TGA TGA-DTA sample sample carrier carrier

61 Calibration

Calibration is a fundamental standard materials which are requirement for thermoanalytical well known. investigations. The knowledge of a quantitatively defined relationship Experimental conditions of calibration between the value indicated by the and measurement should be matched measuring instrument and the correct as closely as possible: not only the value is essential. quantity of energy to be measured must be similar but the site and kinetics Calibration of modern Differential of the generation and temperature Scanning Calorimeters (DSC) and range should be as close as possible Simultaneous Thermal Analyzers (STA) in both calibration and measurement is achieved by quantification of the experiments. produced signal when a known quantity of energy is generated within the All the results of subsequent system. measurements depend on the validity of the calibration. Therefore, it is The calibration procedure consists mandatory to carefully carry out all of measuring thermal properties of calibration procedures.

Thermal Conductivity of Crucible

Type of Instrument DSC/TGA CALIBRATION INFLUENCING FACTORS

Kind & Dimension of Crucible Mass of Sample

62 DSC/(uV/mg) Crucible Selection [2]↓ Exo 8.00 Crucible material: DSC and STA (TGA-DSC/DTA) 7.00 Al Sample: Indium measurements are strongly influenced by Sample mass: between 13.6 and 14.4 mg Pt 6.00 2nd heating Stainless steel the crucible material. The measurements 5.00 Al2O3 shown here on indium in Al, Pt, stainless steel and Al O crucibles clearly 4.00 2 3 demonstrate that both the thermal 3.00 conductivity and the mass of the crucible 2.00 have an effect on the DSC and DTA

1.00 peak shape. The calibration procedures take these effects into consideration and 0 eliminate the influence of the crucible -1.00 material on the measurement results. 140.0 145.0 150.0 155.0 160.0 165.0 170.0 175.0 180.0 Temperature /°C

Indium measurements in different crucible materials

Heating & Cooling Rate

Type of Cooling System DSC/TGA CALIBRATION INFLUENCING FACTORS

Type & Flow Rate of Purge Gas

63 Calibration Materials and Kits

Calibration Materials Calibration Materials

Crucible Materials Reference materials must be Stain-

homogeneous and stable, and the Al2O3 C SiO2 Al Ag Au less Pt W certified values must be accurate. Finding Steel a material that can be used as a reference C H -64.5°C          for more than one property is one of 10 16 the goals of current research. Various H2O 0.0°C - -       - calibration kits and individual standards are available for each thermoanalytical Biphenyl 69.2°C    method presented (DSC, TGA and STA) RbNO 104.2°C !     allowing the instrument to be calibrated 3 Benzoic across its entire temperature range and 122.4°C    acid allowing for the use of different crucible types. The table gives an overview In 156.6°C     - !  ! of possible combinations of calibration Sn 231.9°C     - - ! - and crucible materials. Bi 271.4°C   - -  - 

KClO4 300.8°C     

Pb 327.5°C     - -  - !

Zn 419.5°C     - - - - 

Ag2SO4 426.4°C   - 

CsCl 476.0°C      

Li2SO4 578.0°C      

Al 660.3°C   ! - - - - - 

Common Calibration Materials/Phase Transition Temperature Common Calibration Materials/Phase Transition K2CrO4 668.0°C  -  - 

BaCO3 808.0°C  - - - - 

Ag 961.8°C    - - - - - 

Au 1064.2°C  -  - - - - - 

Ni 1455.0°C ! ------

 No solubility or effects on the melting temperature expected ! Corrosion reactions possible with negligible changes in the melting temperature - Melt or transformation product reacts with the crucible material. Changes in the melting temperature can be expected. � Compatibility unknown

64 Calibration Kits for DSC and DTA

Various calibration kits for different materials transition temperatures (e.g., Mass calibration of the TGA systems temperature ranges, methods, and melting point), lid perforation, and can usually be done automatically with crucible materials are available. The compatibility with crucible material. an internal weight. For temperature following tables show the common These kits are used for temperature and calibration via the c-DTA® feature, the calibration kits for DSC and DTA enthalpy calibration. DSC/DTA calibration kits can be used. measurements with their order numbers,

DSC Sets for Cp, Sensitivity and Enthalpy Calibration

Material Disc Æ Thickness For crucible type Order No.

Sapphire 6 mm 0.25, 0.5, 0.75, 1.0 mm Metallic 6.235.1-91.1.00 0.5, 1.0 mm Al2O3 6 mm Sapphire 5.2 mm 0.25, 0.5, 0.75, 1.0 mm 6.235.1-91.2.00 Al O 0.5, 1.0 mm 2 3 Al2O3 5.2 mm Sapphire 4 mm 0.25, 0.5, 0.75, 1.0 mm Cold-weldable 6.239.2-91.5.00 0.5, 1.0 mm Al2O3 4 mm Al crucibles

DSC/DTA Set* for the Use in Al2O3 Crucibles Individual Substances in Glass Vials Order No.: 6.223.5-91.3.00

Transition (°C) Material Quantity Single Order No.

156.6 Indium In 400 mg 6.223.5-91.3.01 231.9 Tin Sn 400 mg 6.223.5-91.3.02 271.4 Bismuth Bi 400 mg 6.223.5-91.3.04 419.5 Zinc Zn 400 mg 6.223.5-91.3.03 660.3 Aluminum wire Al 400 mg 6.223.5-91.3.05 961.8 Silver wire Ag 400 mg 6.223.5-91.3.06 1064.2 Gold wire Au 400 mg 6.223.5-91.3.07 1455.0 Nickel wire Ni 400 mg 6.223.5-91.3.08 * Standard set can be used with high-pressure DSC

65 Calibration Materials and Kits

DSC Standard Set* – Substances in Sealed Al Crucibles Order No.: 6.239.2-91.3.00 (Volume 25 μl, sample mass minimum 10 mg) For HP-DSC also

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane** C10H16 n/a 156.6 Indium In x n/a 231.9 Tin Sn x n/a 271.4 Bismuth Bi x n/a 419.5 Zinc Zn x n/a 476.0 Cesium chloride CsCl x n/a * Standard set can be used with high-pressure DSC ** HP-DSC: only atmospheric pressure

DSC Low Pressure Set – Substances in Al Low-Pressure Crucibles Order No.: 6.240.10-90.3.00 (Volume 35 μl, max. 3 bar, sample mass minimum 10 mg)

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane C10H16 n/a 156.6 Indium In x n/a 231.9 Tin Sn x n/a 271.4 Bismuth Bi x n/a 419.5 Zinc Zn x n/a 476.0 Cesium chloride CsCl x n/a

DSC High-Pressure Set – Substances in CrNi Steel Crucibles Order No.: 6.240.1-91.4.00 (Volume 27 μl, max. 100 bar, sample mass minimum 10 mg)

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane C10H16 n/a 156.6 Indium In n/a 231.9 Tin Sn n/a 271.4 Bismuth Bi n/a 419.5 Zinc Zn n/a 476.0 Cesium chloride CsCl n/a

66 DSC High-Pressure Set – Substances in CrNi Steel Crucibles Order No.: 6.240.1-91.5.00 (Volume 100 μl, sample mass minimum 10 mg)

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane C10H16 n/a 156.6 Indium In n/a 231.9 Tin Sn n/a 271.4 Bismuth Bi n/a 476.0 Cesium chloride CsCl n/a

DSC Medium-Pressure Set – Substances in CrNi Steel Crucibles Order No.: 6.240.1-91.6.00 (Volume 120 μl , max. 20 bar, sample mass minimum 10 mg)

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane C10H16 n/a

0.0 Water H2O n/a 156.6 Indium In n/a 231.9 Tin Sn n/a

DSC μ-Sensor Set* – Substances in Al Crucibles (volume 25 μl) Order No.: 6.240.3-91.3.00

Transition (°C) Material Pierced lid Single Order No.

-64.5 Adamantane C10H16 n/a 156.6 Indium In x n/a 231.9 Tin Sn x n/a 271.4 Bismuth Bi x n/a * Calibration set only for DSC F1 with μ-sensor

67 Calibration Materials and Kits

DSC/DTA Individual Substances in Glass Vials for Use in Pt Crucibles

Transition (°C) Material Quantity Single Order No.

69.2 Biphenyl* C12H10 500 mg 6.223.5-91.2.01

122.4 Benzoic acid C6H5COOH 500 mg 6.223.5-91.2.02

164.2 Rubidium nitrate* RbNO3 500 mg 6.223.5-91.2.03

300.8 Potassium perchlorate* KClO4 500 mg 6.223.5-91.2.04

426.2 Silver sulfate AgSO4 500 mg 6.223.5-91.2.08 476.0 Cesium chloride CsCl 500 mg 6.223.5-91.2.05

668.0 Potassium chromate* K2CrO4 500 mg 6.223.5-91.2.06

808.0 Barium carbonate Ba CO3 500 mg 6.223.5-91.2.07 * Hazardous material

DSC/DTA Set for the Use in Al2O3 Crucibles, Individual Substances in Glass Vials Order No.: 6.223.5-91.1.00

Transition (°C) Material Quantity Single Order No.

-64.5 Adamantane (Powder) C10H16 400 mg 6.217.1-92.1.09 156.6 Indium In 400 mg 6.223.5-91.3.01 231.9 Tin Sn 400 mg 6.223.5-91.3.02 271.4 Bismuth Bi 400 mg 6.223.5-91.3.04 419.5 Zinc Zn 400 mg 6.223.5-91.3.03 476.0 Cesium chloride CsCl 500 mg 6.223.5-91.2.05 660.3 Al wire Al 400 mg 6.223.5-91.3.05

Calibration Kits for TGA and STA

Temperature Calibration via Magnetic Transitions

TG 209 F1 Libra® Order Number

6 Curie Standards 6.221.2-91.1.00 Calibration supplememt for magnetic transition 6.220.10-93.1.00

STA 449 F1/F3 Jupiter® Order Number

6 Curie Standards 6.221.2-91.1.00 Calibration supplememt for magnetic transition HTP40000A96.010-00

68 ® c-DTA Set* (TGA) for the Use in Al2O3 Crucibles, Substances in Glass Vials Order No.: 6.221.5-91.1.00

Transition (°C) Material Pierced lid Single Order No.

156.6 Indium In 400 mg 6.223.5-91.3.01 231.9 Tin Sn 400 mg 6.223.5-91.3.02 271.4 Bismuth Bi 400 mg 6.223.5-91.3.04 419.5 Zinc Zn 400 mg 6.223.5-91.3.03 660.3 Aluminum wire (ø 1 mm) Al 400 mg 6.223.5-91.3.05 961.8 Silver wire (ø 0.5 mm) Ag 400 mg 6.223.5-91.3.06

* For the use of the c-DTA® set in the TG 209 F1 Libra® please order as well gold, order no. 6.223.5-91.3.07

There are various reference materials which can be used for c-DTA® calibration routines.

c-DTA® calibration in the TG 209 F1 and F3 systems. Excellent coupling of the Platinel sensor with the crucible guarantees that the influence of the heating rate will be small.

69 Chemical Behavior of Pt, Al2O3 and Graphite Crucibles and Sensors

Environmental Effects: Chemical Behavior of Crucibles and Sensors

Made of Pt, Al2O3 and C

In practice, the service life of sensors The following lists also serve to illustrate (thermocouples) and crucibles is most how important regular inspections and heavily impacted by interactions with calibration measurements are. the environment. Diffused impurities, released from the samples, change the These overviews are not exhaustive, but thermal tension or may even cause meant rather as a guideline for the user. initial cracking of the thermocouple wire The temperatures given are primarily and crucible wall. literature values. Temperatures under test conditions might shift to lower The following tables give some details values. It is always advisable to run on the chemical compatibility of preliminary tests in separate furnaces.

DSC sample carrier Pt, Al2O3 and C thermocouples and type S (Pt-Pt10%Rh) crucibles with other sample materials and gas atmospheres.

Chemical Behavior of Platinum (Pt)

Critical No resistance Limited resistance

Halogens (Cl2, F2, Br2), aqua regia Mixtures of KNO3 and NaOH KHF2, LiF2, NaCl at 900°C

Li2CO3, prior to emission of CO2 at 700°C under exclusion Mixtures of NaOH and

PbO, FeCl2 of air NaNO3 at 700°C under

Be alloys (evaporation) Mixtures of KOH and K2S at exclusion of air HCl with oxidants (e.g., chromic acid, manganates, iron (III) and 700°C under exclusion of air

molten salts); reducing atmospheres LiCl at 600°C; MgCl2,

Metals and metal vapors (e.g., B, Pb, Zn, Sn, Ag, Au, Li, Na, K, Sb, Bi, Ba(NO3)2 at 700°C

Ni, Fe, etc.; Se > 320°C (evaporation) HBr, HI, H2O2 (30%); HNO3 Metals and metal oxides with reducing substances such as C, organic at 100°C

compounds or H2 KCl decomposition products Oxides in an inert gas atmosphere at higher temperatures (reduction) which form during melting Sulfur (roughening of the surface, embrittlement) at 768°C Alkali hydroxides, -carbonates, -sulfates, -cyanides and rhodanides at higher temperatures

KHSO4 at higher temperatures Carbon black or free carbon >1000°C

SiO2 under reducing conditions

SiC and Si3N4 >1000°C (release of elementary Si) HBr, KCl solution at high temperatures

70 Chemical Behavior of Alumina (Al2O3) Chemical Behavior of Graphite (C)

Critical Critical

N2 in the presence of carbon (formation of AlN; not O2: reaction above 400°C

recommended to measure carbon black in N2 atmosphere at N2: reaction starting at 1700°C (formation of small amounts elevated temperatures) of cyanides)

F2: formation of AlF3 and O2 Oxides

Cl2: formation of AlCl3 at >700°C Water vapor

Sulfur: no reaction with liquid sulfur; formation of sulfides occur F2, Br2: reaction at room temperature in the presence of carbon in the gas phase Sulfur

H2S: when heated, formation of Al2S3 Si: formation of SiC at approx. 1400°C C: formation of carbides and Al above 1400°C Chromic acid

HF: reaction to AlF3 and H2O at higher temperatures Chlorosulfonic acid ClSo3H

CuSO4: above 1000°C, diffusion through the bottom of the SiO2: formation of SiC: formation of SiC via intermediate crucible product SiO (technical production of SiC above 1800°C;

Compounds containing Si, e.g., MoSi2; contamination of however, reaction between SiO2 and C begins at lower

Al2O3 > 1200°C temperature). -3 Metal fluorides: formation of [AlF6] anions and salts similar to Nitrous gases (NO, NO2)

cryolites Sulfuric acid, H2SO4: concentrated acid critical above 150°C,

SiO2 glass: melt dissolves Al2O3 fuming acid already at room temperature

Hydrogen sulfates of alkaline metals and alkaline-earth metals Nitric acid, HNO3: diluted acid critical at 90°C, fuming acid HCl: above 600°C, reactions in the presence of carbon already at room temperature

B2O3 (Borax): melt dissolves Al2O3; formation of Al-borates SO3: critical above 100°C

and -borides Danger of explosion with perchloric acid, HClO4 Alkaline and alkaline-earth oxides and their salts with volatile NaOCl: critical above 50°C anions; important for hydroxides, nitrides, nitrates, carbonates, peroxides, etc.

CaC2: when heated, formation of Al4C2 PbO: reaction above 700°C

UO3: reaction starts at 450°C MeIIO: Me= Fe2+, Cu2+, Ni2+, etc., formation of spinels, CaO formation above 1200°C

Alkaline and alkaline-earth ferrites: melt dissolves Al2O3 Ti-alloys (very high oxygen affinity) Reactions with Fe-Ni- and Mg-alloys possible at higher temperatures

71 Material Compatibility – Sample in Crucible

Material Compatibility

The right crucible must always be These tables serve to indicate which chosen for the given experiment. of the common crucible types can be Crucible materials should be specially used for each application, including selected depending on the application ceramics, metals, inorganics and other and sample materials in order to prevent more general applications. reactions between the sample and crucible.

General Applications

Al O crucible Materials/ 2 3 Pt/Rh Al O Al Pt+Al O liner sprayed with Graphite Crucible Types 2 3 2 3 Y2O3 Clays  *  * * No Minerals  *  * * No Oxide ceramics  *  * * No Salts  No  No No No Glasses  No  No No * Metals No**  No   No Polymers       Carbon materials * *  * *  Inorganics * * * * * *

Ceramics

Al O crucible Materials/ 2 3 Pt/Rh Al O Al Pt+Al O liner sprayed with Graphite Crucible Types 2 3 2 3 Y2O3

Alumina (Al2O3)      *

Zirconia (ZrO2)      *

Y2O3 or MgO      *

Silicon dioxide (SiO2)  No  No No No

Silicon nitride (Si3N4) No *  * * * Aluminum nitride * * * * * * (AlN) Boron nitride (BN) * * * * * * Silicon carbide (SiC) No * * * * Titanium oxide      * (TiO2)

72 Metals

Al O crucible Materials/ 2 3 Pt/Rh Al O Al Pt+Al O liner sprayed with Graphite Crucible Types 2 3 2 3 Y2O3 Al and Al-alloys No**  No    Mg and Mg-alloys No** * No * *  Cu and Cu-alloys No**  No  *  Fe and Fe-alloys No** * No *  No Ni and Ni-alloys No** * No *  No Ti and Ti-alloys No** * No *  No Sn and Sn-alloys No**  No    Au- and Ag-alloys No**  No   * Cr-, Mo-, Co-alloys No** * No *  No

Inorganics

Al O crucible Materials/ 2 3 Pt/Rh Al O Al Pt+Al O liner sprayed with Graphite Crucible Types 2 3 2 3 Y2O3 Silicon No No  No No * Iron oxide  No  No No No Lead oxide No * * * * No Magnesium fluoride  No  No No No information Calcium fluoride  No  No No  Copper oxide  No  No No No Graphites * * * * *  Carbonates  *  * * No Sulphates  *  * * No

 No reaction expected * Reactions possible at high temperatures No** Not recommended; reactions may occur prior to or during melting. This could lead to damage to the crucible and/or sensor. Extreme caution advised.

73 Recommendations for Cleaning Al2O3 and Pt Crucibles

Recommendations for Cleaning Al2O3 and Pt Crucibles

In most cases, the majority of ceramic following cleaning recommendations and metallic crucibles and their lids are given for the most common

can be reused many times. In order to crucibles, made of alumina (Al2O3) and ensure a long lifetime of proper use, the platinum (Pt).

Acids must be handled very carefully under a fume hood. Use protective glasses, gloves and apron and read the MSD sheets. Acids should only ever be handled by a person experienced in the handling of chemicals.

All acids (especially HF) are very dangerous and can cause extremely serious injuries or death if they come in contact with the skin or are inhaled.

Work with acids is at the user’s own risk. NETZSCH can assume no liability for damage or injury resulting from the use of acids.

74 Recommendations for Cleaning Al2O3 and Pt Crucibles

Al2O3 Crucibles Pt Crucibles

Contamination with organics Contamination with organics (polymers, organic pyrolysis (polymers, etc.) products, carbon black, etc.) Heat crucibles in air or oxygen Heat crucibles in air or oxygen to approx. 900°C to burn off the to approx. 900°C to burn off the organics. If oxide fillers are present, organics. attempt to remove them mechan- If there are oxide fillers present, be ically or use HF (see next procedure). careful with the end temperature, as there might be a reaction with Contamination with metals and alumina (lower the temperature and alloys work in oxygen). Use a separate There is often no way of removing furnace, if available. metals, as Pt will alloy with most metals at higher temperatures. Contamination with metals However, make an attempt with HCl and alloys acid (concentration 25% or higher). Clean with HCl acid (concentration If there is no reaction with the 25% or higher). If there is no contaminant, try heating the beaker reaction with the contaminant, heat with the acid.

the beaker with the acid. If HCl alone Do not use a mixture of HCl/HNO3 does not work, use a mixture of (1:1). This would also dissolve the Pt!

HCl/HNO3 (1:1) (both concentrated). This may be heated as well. Oxides and other salts Some salts are water soluble. Boil the Oxides and other salts crucibles in distilled water. Some salts are water soluble. Boil the Most oxides can be dissolved in HF. crucibles in distilled water. In some cases, it is helpful to warm

Use HCl or a mixture of HCl/HNO3 the acid. (1:1) (both concentrated). Some salts can be dissolved in HCl. Oxides are often very stable or have already reacted with the alumina. It could easily be the case that it is impossible to remove the deposits. In that case, the crucible must be discarded. HF dissolves oxides, but also the alumina.

Following these cleaning procedures, rinse the crucibles several times with distilled water and let them dry at room temperature. Then heat them in a separate furnace in air to 1500°C.

75 The NETZSCH Group is a mid-sized, family-owned German company engaging in the manufacture of machinery and instrumentation with worldwide production, sales, and service branches.

The three Business Units – Analyzing & Testing, Grinding & Dispersing and Pumps & Systems – provide tailored solutions for highest-level needs. Over 3,000 employees at 163 sales and production centers in 28 countries across the globe guarantee that expert service is never far from our customers.

When it comes to Thermal Analysis, Adiabatic & Reaction Calorimetry and the determination of Thermophysical Properties, NETZSCH has it covered. Our 50 years of applications experience, broad state-of-the-art product line and comprehensive service offerings ensure that our solutions will not only meet your every requirement but also exceed your every expectation.

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[email protected] www.netzsch.com subject to change. specifications are Systems · EN 1000 0214 LH Technical DSC, TGA and STA NGB · Accessories for